WO2013149001A2 - Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof - Google Patents

Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof Download PDF

Info

Publication number
WO2013149001A2
WO2013149001A2 PCT/US2013/034347 US2013034347W WO2013149001A2 WO 2013149001 A2 WO2013149001 A2 WO 2013149001A2 US 2013034347 W US2013034347 W US 2013034347W WO 2013149001 A2 WO2013149001 A2 WO 2013149001A2
Authority
WO
WIPO (PCT)
Prior art keywords
optionally substituted
halo
independently
alkyl
alkylthio
Prior art date
Application number
PCT/US2013/034347
Other languages
French (fr)
Other versions
WO2013149001A3 (en
Inventor
Mingqian He
Jieyu Hu
Weijun Niu
Adama TANDIA
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to EP13717903.2A priority Critical patent/EP2831078A2/en
Priority to JP2015503575A priority patent/JP2015519300A/en
Priority to US14/387,102 priority patent/US20150045560A1/en
Priority to CN201380018052.5A priority patent/CN104797583A/en
Publication of WO2013149001A2 publication Critical patent/WO2013149001A2/en
Publication of WO2013149001A3 publication Critical patent/WO2013149001A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/18Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving halogen atoms of halogenated compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/30Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/16Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D403/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D495/00Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/0803Compounds with Si-C or Si-Si linkages
    • C07F7/0825Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083Syntheses without formation of a Si-C bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10Organic polymers or oligomers
    • H10K85/111Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10Organic polymers or oligomers
    • H10K85/151Copolymers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40Organosilicon compounds, e.g. TIPS pentacene
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
    • C08G2261/12Copolymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3229Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing nitrogen and sulfur as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50Physical properties
    • C08G2261/51Charge transport
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50Physical properties
    • C08G2261/59Stability
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90Applications
    • C08G2261/92TFT applications
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90Applications
    • C08G2261/95Use in organic luminescent diodes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
    • H10K10/484Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • OSCs have attracted a great amount of attentions in the research community due to their advantages over inorganic semiconductors such as processing in any form, exhibiting a high mechanical flexibility, producing at low cost, and having a low weight.
  • Polycyclic aromatic compounds such as oligothiophenes, acenes, rylenes, phthalocyanens, and polythiophene, have been widely studied as semiconductor materials.
  • Embodiments comprise a rationally designed a family of alkyl-substituted fused naphthalene hetero ring materials.
  • the materials have several advantages in that it is easier to introduce substituents onto the fused rings allowing for significant improvement of the polymerization process and the polymer material processibility; substituents can be introduced to multiple positions which allows for fine tuning material packing behaviors; introduction of substituted pyrrole structures into the substituted naphthalene results in lower reorganization energy and higher mobility; and introduction of ⁇ -substituents on five member ring increases the material stability.
  • a first embodiment comprises a compound of formula:
  • each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C 2 - C40 alkenyl, optionally substituted C2-C40 alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, optionally substituted heterocyclyl, or an optionally substituted aryl or optionally substituted heteroaryl from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or naphthyridinyl.
  • each Xi is independently NRi, PRi, AsRi, Sb, O, S, Se, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri and each X 2 is independently N, P, As, or SiRi, with the proviso that due to conjugation, X 2 may be bonded to one or more additional Ri. In some embodiments, each X 2 is independently N or CRi, with the proviso that due to conjugation, X 2 may be bonded to one or more additional Ri .
  • the compound comprises la, lb, 2a, 2b, or 2c, and the hole reorganization energy is less than 0.35 eV. In some embodiments, the hole reorganization energy is from about 0.05 to about 0.35 eV.
  • m is 1, 2, or 3; o is 0, 1, 2, or 3; R c i, R c2 , Rc3, and are independently H, halo, optionally substituted C 1 -C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C 2 -C 4 o alkenyl, optionally substituted C 2 -C 4 o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
  • Xi is NR h PR h AsRi, Sb, O, S, Se, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri;
  • X 2 is N or CRi, with the proviso that due to conjugation, X 2 may be bonded to one or more additional Ri;
  • y is H, halo, optionally substituted Ci-C 4 o alkyl, optionally substituted C 2 -C 4 o alkenyl, optionally substituted C 2 -C 4 o alkynyl, halo, OSO- alkyl, Mg-halo, Zn-halo, Sn(alkyl) 3 , B(OH) 2 , or B(alkoxy) 2 ; and each Ri is independently H, halo, optionally substituted Ci-C 4 o alkyl,
  • each Ri is independently H, halo, optionally substituted Ci-C 4 o alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C 2 -C 4 o alkenyl, optionally substituted C 2 -C 4 o alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, optionally substituted heterocyclyl, or an optionally substituted aryl or optionally substituted heteroaryl from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or naphthyridinyl.
  • Another embodiment comprises a method of synthesizing a compound comprising:
  • each Ri is independently H, halo, optionally substituted C 1 -C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C 2 -C40 alkenyl, optionally substituted C 2 -C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, or Se;
  • Another embodiment comprises a method of making a compound of structure:
  • Another embodiment comprises a method of making a polymer of structure:
  • Another embodiment comprises a device comprising compound la, lb, 2a, 2b, or 2c.
  • Another embodiment comprises a device comprising polymer la', lb', 2a', 2b', 2c' or 2d'.
  • FIG. 1 shows the importance the reorganization energy (R.E.) and the transfer integral in the charge carrier mobility (M). Based on the various plots shown for transfer integrals from 0.4 to 2.0 eV, it is clear that large increases in the transfer integral do not yield significant variation in the mobility, unless the reorganization energies are small.
  • Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • a weight percent of a component is based on the total weight of the formulation or composition in which the component is included.
  • alkyl refers to a monoradical branched or unbranched saturated hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. This term is exemplified by groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-hexyl, n-decyl, tetradecyl, and the like.
  • substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and - S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkyl group as defined above that is interrupted by 1-10 atoms independently chosen from oxygen, sulfur and NR a , where R a is chosen from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl and heterocyclyl.
  • All substituents may be optionally further substituted by alkyl, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, or -S(0) n Rso, in which R S o is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (3) an alkyl group as defined above that has both 1, 2, 3, 4 or 5 substituents as defined above and is also interrupted by 1-10 atoms as defined above.
  • alkylene refers to a diradical of a branched or unbranched saturated hydrocarbon chain, having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, typically 1-10 carbon atoms, more typically 1, 2, 3, 4, 5 or 6 carbon atoms.
  • This term is exemplified by groups such as methylene (-CH 2 -), ethylene (-CH2CH2-), the propylene isomers (e.g., -CH 2 CH 2 CH 2 - and -CH(CH 3 )CH 2 -) and the like.
  • substituted alkylene refers to: (1) an alkylene group as defined above having 1, 2, 3, 4, or 5 substituents selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, amino carbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-hetero
  • substituents may optionally be further substituted by 1 , 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkylene group as defined above that is interrupted by 1-20 atoms independently chosen from oxygen, sulfur and NR a -, where R a is chosen from hydrogen, optionally substituted alkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl and heterocyclyl, or groups selected from carbonyl, carboxyester, carboxyamide and sulfonyl; or (3) an alkylene group as defined above that has both 1, 2, 3, 4 or 5 substituents as defined above and is also interrupted by 1-20 atoms as defined above.
  • alkoxy refers to the group R-0-, where R is an optionally substituted alkyl or optionally substituted cycloalkyl, or R is a group -Y-Z, in which Y is optionally substituted alkylene and Z is optionally substituted alkenyl, optionally substituted alkynyl; or optionally substituted cycloalkenyl, where alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl are as defined herein.
  • Typical alkoxy groups are optionally substituted alkyl-O- and include, by way of example, methoxy, ethoxy, n- propoxy, iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2- dimethylbutoxy, trifiuoromethoxy, and the like.
  • alkylthio refers to the group Rs-S-, where Rs is as defined for alkoxy.
  • alkenyl refers to a monoradical of a branched or unbranched unsaturated hydrocarbon group typically having from 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms and even more typically 2 to 6 carbon atoms and having 1-6, typically 1, double bond (vinyl).
  • substituted alkenyl refers to an alkenyl group as defined above having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -
  • alkynyl refers to a monoradical of an unsaturated hydrocarbon, typically having from 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms and even more typically 2 to 6 carbon atoms and having at least 1 and typically from 1-6 sites of acetylene (triple bond) unsaturation.
  • Typical alkynyl groups include ethynyl, (- C ⁇ CH), propargyl (or prop-l-yn-3-yl, -CH 2 C ⁇ CH), and the like. In the event that alkynyl is attached to nitrogen, the triple bond cannot be alpha to the nitrogen.
  • substituted alkynyl refers to an alkynyl group as defined above having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl
  • substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • acylamino refers to the group -NR NCO C(0)R where each R NCO is independently hydrogen, alkyl, aryl, heteroaryl, or heterocyclyl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • aryl refers to an aromatic carbocyclic group of 6 to 20 carbon atoms having a single ring (e.g., phenyl) or multiple rings (e.g., biphenyl), or multiple condensed (fused) rings (e.g., naphthyl or anthryl).
  • Typical aryls include phenyl, naphthyl and the like.
  • such aryl groups can optionally be substituted with from 1 to 5 substituents, typically 1 to 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO
  • substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • amino refers to the group -NH 2 .
  • substituted amino refers to the group -NR W R W where each R w is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, carboxyalkyl (for example, benzyloxycarbonyl), aryl, heteroaryl and heterocyclyl provided that both R w groups are not hydrogen, or a group -Y-Z, in which Y is optionally substituted alkylene and Z is alkenyl, cycloalkenyl, or alkynyl.
  • substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and - S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • Carboxyalkyl refers to the groups -C(0)0-alkyl or -C(0)0- cycloalkyl, where alkyl and cycloalkyl, are as defined herein, and may be optionally further substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, in which R S o is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • cycloalkyl refers to carbocyclic groups of from 3 to 20 carbon atoms having a single cyclic ring or multiple condensed rings.
  • Such cycloalkyl groups include, by way of example, single ring structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and the like, or multiple ring structures such as adamantanyl, bicyclo [2.2.1] heptane, l,3,3-trimethylbicyclo[2.2.1]hept-2-yl, (2,3,3- trimethylbicyclo[2.2.1]hept-2-yl), or carbocyclic groups to which is fused an aryl group, for example indane, and the like.
  • cycloalkenyl refers to carbocyclic groups of from 3 to 20 carbon atoms having a single cyclic ring or multiple condensed rings with at least one double bond in the ring structure.
  • substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • heteroaryls include, but are not limited to, [l,2,4]oxadiazole, [l,3,4]oxadiazole, [l ,2,4]thiadiazole, [l,3,4]thiadiazole, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, isoquinoline, quinoline, phthalazine, naphthylpyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, phenanthroline, isothiazole, phenazine, isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline, triazole, oxazo
  • substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • hetero aryloxy refers to the group heteroaryl-O-.
  • heterocyclyl groups can be optionally substituted with 1, 2, 3, 4 or 5, and typically 1, 2 or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, hetero arylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl,
  • substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF 3 , amino, substituted amino, cyano, and -S(0) n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
  • thiol refers to the group -SH.
  • substituted alkylthio refers to the group -S-substituted alkyl.
  • heteroarylthiol refers to the group -S-heteroaryl wherein the heteroaryl group is as defined above including optionally substituted heteroaryl groups as also defined above.
  • sulfoxide refers to a group -S(0)Rso, in which R S o is alkyl, aryl, or heteroaryl.
  • substituted sulfoxide refers to a group -S(0)Rso, in which R S o is substituted alkyl, substituted aryl, or substituted heteroaryl, as defined herein.
  • sulfone refers to a group -S(0) 2 Rso, in which R S o is alkyl, aryl, or heteroaryl.
  • substituted sulfone refers to a group - S(0) 2 Rso, in which R S o is substituted alkyl, substituted aryl, or substituted heteroaryl, as defined herein.
  • keto refers to a group -C(O)-.
  • thiocarbonyl refers to a group -C(S)-.
  • conjugated group is defined as a linear, branched or cyclic group, or combination thereof, in which p-orbitals of the atoms within the group are connected via delocalization of electrons and wherein the structure can be described as containing alternating single and double or triple bonds and may further contain lone pairs, radicals, or carbenium ions.
  • Conjugated cyclic groups may comprise both aromatic and non-aromatic groups, and may comprise polycyclic or heterocyclic groups, such as diketopyrrolopyrrole. Ideally, conjugated groups are bound in such a way as to continue the conjugation between the thiophene moieties they connect.
  • each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • any subset or combination of these is also specifically contemplated and disclosed.
  • the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions.
  • steps in methods of making and using the disclosed compositions are if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
  • Embodiments comprise a rationally designed a family of alkyl-substituted fused naphthalene hetero ring materials.
  • the materials have several advantages in that it is easier to introduce substituents onto the fused rings allowing for significant improvement of the polymerization process and the polymer material processibility; substituents can be introduced to multiple positions which allows for fine tuning material packing behaviors; introduction of substituted pyrrole structures into the substituted naphthalene results in lower reorganization energy and higher mobility; and introduction of ⁇ -substituents on five member ring increases the material stability.
  • compositions comprising the formula la, lb, 2a, 2b, or 2c:
  • each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X 2 is independently N, P, As, SiRi, or CRi with the proviso that due to conjugation, X 2 may be bonded to one or more additional Ri; y is H, halo, trialkylsilane, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally
  • Each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C 2 -C4o alkenyl, optionally substituted C 2 -C4o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
  • y is H, halo, -OSO-alkyl, -Mg-halo, -Zn-halo, - Sn(alkyl) 3 , -B(OH) 2 , or -B(alkoxy) 2 .
  • each Ri is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or aralkyl.
  • each Ri is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or optionally substituted phenyl, optionally substituted thiophenyl, optionally substituted furanyl, optionally substituted pyrrolyl, optionally substituted imidazolyl, optionally substituted triazolyl, optionally substituted oxaxolyl, optionally substituted thiazolyl, optionally substituted napthalenyl, optionally substituted isoquinolinyl, optionally substituted quinolinyl, or optionally substituted naphthyridinyl.
  • each Xi is independently NRi, PRi, AsRi, Sb, O, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; and each X 2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X 2 may be bonded to one or more additional Ri.
  • each Xi is independently NRi, PRi, AsRi, Sb, O, S, Se, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri and each X 2 is independently N, P, As, or SiRi, with the proviso that due to conjugation, X 2 may be bonded to one or more additional Ri .
  • composition comprises formula la', lb', 2a', 2b', 2c', or 2d':
  • n is an integer greater than zero; Xi, X 2 , y, and Ri all have the same meanings as above; k is from 1 to 10 with the proviso that when m is 0 (meaning no comonomer is present), k is null (meaning that the "k” term vanishes as it would become equivalent to the "n” term - therefore the polymer comprises "n" fused heterocyclic naphthalene groups as described by la', lb', 2a', 2b', 2c', or 2d'); m is from 0 to 10; the ratio of k to m may be from 1 : 10 to 10: 1 with the exception that when m is 0 the ratio of k to m is null; and n is from about 1 to 500.
  • k is 1 , 2 or 3.
  • m is 1 , 2, or 3.
  • the ratio of k to m is from about 3 : 1 to about 1 :3.
  • n is from about 3 to about 20, about 3 to about 15, about 3 to about 12, about 3 to about 10, or about 5 to about 9.
  • n is about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, or 500.
  • Comonomer as used herein, describes a conjugated system such as any aromatic structure, double or triple bonds, or conjugated structures.
  • Examples of comonomers include, but are not limited to:
  • R c i , Rc 2 , Rc3, and R c4 are independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or aralkyl.
  • Rci , Rc 2 , Rc3, and Rc 4 are independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or optionally substituted phenyl, optionally substituted thiophenyl, optionally substituted furanyl, optionally substituted pyrrolyl, optionally substituted imidazolyl, optionally substituted triazolyl, optionally substituted oxaxolyl, optionally substituted thiazolyl, optionally substituted napthalenyl, optionally substituted isoquinolinyl, optionally substituted quinolinyl, or optionally substituted naphthyridinyl.
  • embodiments may be produced through a series of synthetic steps.
  • reaction Schemes 1-7 depicted below provide potential routes for synthesizing the embodiments as well as key intermediates.
  • the methods disclosed in the instant Schemes and Examples are intended for purposes of exemplifying only and are not to be construed as limitations thereon.
  • a naphthalene diol compound, (1) may be reacted with N-bromosuccinimide in THF at a 1 :2 ratio, and quenched with saturated sodium thiosulfate to produce l,5-dibromonaphthalene-2,6-diol, (2).
  • Compound (2) may be reacted with an alcohol protecting group, such as excess chloro(methoxy)methane in dichloromethane and diisopropylethylamine, and quenched with water after 22 hours. After extraction, l-5-dibromo-2,6-bis(PG)naphthalene, (3), may be obtained.
  • Compounds of form (3) may be combined with n-butyl lithium (2.4 equiv) in an organic solvent, then combined with a halo-alkyl, such as iodomethane, in THF, extracted with saturated sodium sulfate, washed, dried, and purified to give 3,7,- dibromo-2,6-bis(PG)-l,5-dialkylnaphthalene, compound (4).
  • a halo-alkyl such as iodomethane
  • compound (4) may be combined with n-BuLi (2.4 eq.) in solvent (e.g., anhydrous ethyl ether) at room temperature. After sufficient time, the solution can be cooled to 0°C and a THF solution of diiodine (I 2 ) added. The resulting mixture is allowed to warm to room temperature over time, quenched, and the aqueous layer extracted. The combined organic extracts can be washed and dried to give compound (5) ((5b) in the case of diiodine). After evaporation, the resulting crude product can be purified by column chromatography on silica gel.
  • solvent e.g., anhydrous ethyl ether
  • Compounds of structure (6), 3,7-dihalo-l,5-dialkylnaphthalene-2,6-diol may be produced from compound (5) by combining (5) with 6N HCl in dichloromethane/methanol (1 : 18 ratio), heating, stirring overnight, pouring into water, and extracting with ethyl acetate.
  • Compounds of structure (7a), 3,7-Dihalo-l ,5-dialkylnaphthalene-2,6-diyl bis(trifluoromethanesulfonate), may be formed by reaction of compound (6) in an organic solvent, such as pyridine and dichloromethane, with trifluoromethanesulfonic anhydride (1 :2), mixed with water and 1M HCl, extracted with dichloromethane and concentrated in vacuo. The residue may then be purified to give compound (7a) at about 80% yield.
  • an organic solvent such as pyridine and dichloromethane
  • Compounds (7b) may be formed from compounds (6) by adding Tetrakis(triphenylphosphine)palladium(0) ((Pd(PPh3)4), Cul, triethylamine, diisopropylamine and terminal alkynes to a degassed solution of (6), stirring at 80°C, and adding water and 1M HCl after approximately 15 minutes. The resulting mixture can be extracted and the combined organic layers dried and concentrated to give (7b) (see, e.g., Zhao,Y.; et al. 15 CHEM. EUR. J. 13356 (2009)), incorporated by reference in its entirety).
  • Compounds (8a) may be formed from compounds (7a) by adding bis(triphenyphosphine) palladium chloride ((Pd(PPh 3 ) 2 Cl 2 ), Cul, and terminal alkynes to a degassed solution of (7a) in solvent (e.g., THF or DMF), stirring at room temperature, and adding water and 1M HCl after approximately 1 hour. The resulting mixture can be extracted and the combined organic layers dried and concentrated to give (8a) (see, e.g. Shinamura, S. et al. 133 J. AM. CHEM. SOC. 5024 (2011), incorporated by reference in its entirety).
  • solvent e.g., THF or DMF
  • Compound (9a) may be formed from compound (8a) via reaction of (8a) with tBuONa, tris(dibenzylideneacetone)dipalladium(0), and 2,2'- bis(diphenylphosphino)-l, l'-binaphthyl in dry solvent.
  • Primary amines may be added via a syringe and the mixture was refluxed under nitrogen for 4 h. After cooling to room temperature, water can be added to the solution and the reaction mixture extracted. After drying and solvent evaporation, the residue may be purified to give compound (9a) (see, e.g., Lu et al, 160 SY . METALS 1438-41 (2010), incorporated by reference in its entirety).
  • compound (9a) may be formed from compound (8a) via combination with aryl chloride, amine, KOtBu and a catalyst in 1 ,2- dimethoxyethane.
  • the mixture may be stirred at room temperature in an air atmosphere and monitored by GC/GC-MS.
  • the reaction may be quenched with water, extracted with solvent, dried, concentrated and purified to give the desired product (see, e.g., Lee et al., 13 ORG. LETT. 5540 (2011), incorporated by reference in its entirety).
  • Compound (9b) may be formed from compound (8b) via reaction of (8b) with Cs 2 C0 3 , Tris(dibenzylideneacetone)dipalladium(0), and 2,2'-bis(diphenylphosphino)- ⁇ , ⁇ -binaphthyl in dry solvent.
  • Primary amines may be added via a syringe and the mixture was refluxed under nitrogen for 4 h. After cooling to room temperature, water can be added to the solution and the reaction mixture extracted. After drying and solvent evaporation, the residue may be purified to give compound (9b).
  • compound (9b) may be formed from compound (8b) via reaction of (8b) with Si(SH)(i-Pr) 3 in solvent (Thompson et al, 21 BIOORG. MED. CHEM. LETT. 3764-66 (2011) , herein incorporated by reference), as noted below:
  • R 2 is an alkyl or aryl.
  • the second comprises combining (9a) or (9b) with a ruthenium catalyst in dry/deoxygenated solvent (e.g., THF) in a scintillation vial under an inert atmosphere, such as in a glove box.
  • a ruthenium catalyst in dry/deoxygenated solvent (e.g., THF)
  • THF dry/deoxygenated solvent
  • the mixture can then be sealed and heated ( ⁇ 70°C) for an extended period of time ( ⁇ 2 days), while being monitored for completion of the reaction.
  • the resulting products may be purified by column chromatography ⁇ see, e.g., Nair et al, 16 CHEM. EUR. J. 7992 (2010), incorporated by reference in its entirety).
  • Another method of forming compounds (10a) and (10b) from compounds (9a) and (9b) comprises reacting (9b) or (9a) with NaOH in ethyl acetate and N-methylpyrrolidone at 5C, then allowing the reaction to warm to room temperature for 30 minutes (WO 2011147690, herein incorporated by reference in its entirety).
  • Compounds (10a) and (10b) may be formed from compounds (8a) and (8b), respectively, using a number of different methods.
  • the first is the general cyclization procedure for dibromodiethynylnaphthalene analogues described in Shoji et al, 133 J. AMER. CHEM SOC. 5024-5035 (2011) (incorporated by reference in its entirety).
  • the procedure combines Na 2 S in NMP with (8a) or (8b) and heating to about 185°C for about 12 hours, then adding the solution to a saturated aqueous ammonium chloride solution to precipitate.
  • the precipitate is collected by filtration, washed, and purified by vacuum sublimation to give (10a) or (10b).
  • the resulting products may be extracted and purified by column chromatography.
  • the third method is similar to the second, in that it combines a solution of (8a) or (8b) is combined with Pd 2 DBA 3 , LiHMDS, and 4,5- bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) in dry solvent (e.g., toluene) and stirred under inert atmosphere for a short time ( ⁇ 2 min), then addition of TIPS-SH.
  • the resulting solution may be stirred under inert atmosphere in a microwave at 130°C and 300W until all aryl bromide is consumed as measured by GC-MS.
  • Schemes 2 and 3 are synthetically similar to Scheme 1, but provide for the synthesis of the 2a, 2b, and 2c:
  • Ri and Xi are the same as described in Scheme 1 and R 3 is alkyl (X 2 is shown as -CH, but could be generalized to any X 2 ).
  • polymer precursors (Hal), (Ha2), and (Ha3) may be obtained from (10a), (10c), and (lOd) with the appropriate chemical structure using the same synthetic procedures described below.
  • Possible routes from (10b) to (llbl) include the combination of (10b) (1.5 mmol) with NBS (3.6 mmol) in organic solvent (e.g., chloroform), stirring at room temperature for 24 hours, and subsequent washing (saturated sodium carbonate/water), extraction (DCM), drying with Na 2 S0 4 , and purification (Huang et al., 13 ORG. LETT. 5252 (2011), incorporated by reference in its entirety) or combination of (10b) with slow addition of PyHBr 3 (1 eq.) in solvent (THF/CHC1 3 ) and stirring for approx. 30 minutes at 0°C.
  • organic solvent e.g., chloroform
  • reaction is then diluted with dichloro methane and washed (2x100 mL Na 2 S 2 0 3 ), washed with brine, dried over Na 2 S0 4 , and purified by flash chromatography (gradient eluent 5% EtOAc/hexanes to 20% EtOAc/hexanes) (Qi et al., 133 J. AM. CHEM. SOC. 10050 (2011), incorporated by reference in its entirety, and Luo et al., 5 ORG. LETT.4709-12 (2003), incorporated by reference in its entirety).
  • the mixture may then be quenched with NaHC0 3 , extracted with EtOAc, dried and purified by flash chromatography (Fargeas et al., 9 EUR. J. ORG. CHEM. 1711-21 (2003), incorporated by reference in its entirety).
  • the mixture may then be quenched with H 2 0/NaHC0 3 , extracted, dried and purified via flash chromatography (2:98 EtOAc/petroleum ether) (Avolio et al., 48 J. MED. CHEM. 4547 (2005), incorporated by reference in its entirety).
  • a second route from (10b) to (llb3) is the combination of (1,5- cyclooctadiene)(methoxy)iridium(I) dimmer (0.15 eq.), 4,4'-di-tert-butyl-2,2'-dipyridyl (0.03 eq.), bis(pinacolato)diboron (2.00 eq.), 10b (1 eq.), and a stirring bar in a dry flask under argon. To this mixture is added anhydrous dichloromethane (2.2. mL) to give a colorless suspension and the flask is heated at 65°C.
  • Conversion from (llbl) to (llb3) may be accomplished by a number of routes. The first involves dissolving (llbl) (1.2 mmol) in anhydrous THF (25 mL) or an equivalent solvent and cooling to -78°C, then adding n-butyllithium (2.2. eq.) and stirring. Next, 2-isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (4 eq.) may be added and the reaction stirred overnight.
  • (10a)-(10d) may be combined with dibromide comonomer (1 : 1 ratio), trans-di( ⁇ -acetato)bis[o-(di-o-tolyl-phosphino)benzyl]dipalladium(II) (4% mol) and Cs 2 C0 3 (2 eq.) and placed in a microwave vial with a magnetic stirring bar. The vial is then sealed with a cap and purged with nitrogen to remove the oxygen. THF is added and the reaction is heated with an oil bath at 120°C (reaction under pressure).
  • the polymer may be formed by combining (llb2) (or (lla2)) (0.25 mmol) with ditin, or diboranes or diboronate esters (comonomer) (1 : 1 eq.) in toluene (15 mL). The solution is flushed with argon for 10 min, and then Pd 2 DBA 3 (2 mol%) and P(o-tolyl) 3 (16.36 mg, 8%) are added into the flask. The flask is purged, heated to 110°C, and stirred for 48 h under argon.
  • a second alternative for Scheme 5 is to start with (llb2) or (lla2).
  • (llb2) (0.25 mmol) and the dibromide comonomer (1 : 1 eq.) are dissolved in toluene (15 mL).
  • the solution is flushed with argon for 10 min, and then Pd 2 DBA 3 (2 mol%) and P(o-tolyl) 3 (16.36 mg, 8%) are added into the flask.
  • the flask is purged, heated to 110°C, and stirred for 48 h under argon.
  • the mixture is then cooled to room temperature, and the product filtered, washed with methanol (100 mL) and hexane in a Soxhlet apparatus to remove the oligomers and catalyst residue. Finally, the polymer is extracted with chloroform, condensed by evaporation and precipitated into methanol. The polymer was collected as a dark purple solid (Huo et al., 49 ANGEW CHEM. INT. ED. 1500 (2010), incorporated by reference in its entirety).
  • the polymer in Scheme 5 may be formed by first dissolving (llbl) (or (llal)) in anhydrous THF and then adding n-butyllithium (1.2 eq.) and stirring. 2-Isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (4 eq.) is added and the reaction stirred overnight. The product was extracted, washed, dried and evaporated give (llbl3), which can be purified via with cyclohexane/ethyl acetate (4: 1) column chromatography.
  • Comonomers may be produced by known synthetic methods. Such methods are shown in, for example, 72 J. ORG. CHEM. 442-451 (2007), 6 BEILSTEIN J. ORG. CHEM. 830-845 (2010), Jerry March, Michael B. Smith, MARCH'S ADVANCED ORGANIC CHEMISTRY: REACTIONS, MECHANISMS, AND STRUCTURE (6 th Ed. Wiley- Interscience), Richard C. Larock, COMPREHENSIVE ORGANIC TRANSFORMATIONS (1999 Wiley-VCH), all hereby incorporated by reference in their entireties.
  • embodiments herein are optimized for reorganization energy and mobility.
  • compounds embodied herein have improved solid state properties as a result of lower reorganization energy and/or higher mobility.
  • the properties of the compounds embodied herein may be described by Marcus theory (R.A. Marcus, 65 REV. MOD. PHYS. 599 (1993), herein incorporated by reference in its entirety).
  • T is the temperature
  • is the reorganization energy
  • is the transfer integral
  • h and ks are the Planck and Boltzmann constants, respectively.
  • Fig. 1 schematically depicts the relationship of mobility (M) as a function of the reorganization energy (R.E.) at five different values of the transfer integral (ranging from 0.4 eV to 2 eV). From Fig. 1, it is clear that the difference in mobility for different transfer integrals is only significant for small values of the reorganization energy. A big increase in the transfer integral does not yield a significant variation in the mobility, unless the reorganization energies are small. This implies that any optimization of the mobility should start with the design of single molecules with very low reorganization energy.
  • the reorganization energy includes two contributions that are associated with charge hopping. One is introduced by the geometric changes within the single molecule, and is denoted the internal part. The second one arises from the repolarization changes of the surrounding medium and is usually much smaller than the first one. In studies to qualitatively order molecules it is generally valid to neglect this last contribution in the evaluation of the reorganization energy as no significant solvent reorganization occurs during the charge transfer in the condensed phase.
  • Table 1 incorporates reorganization energies for a number of embodiments.
  • the geometry is optimized using quantum mechanics for both neutral and ionic states. Consequently, the basic hopping step in a molecular wire is defined by four energies: E 0 and E + represent the energies of the neutral and cation species in their lowest energy geometries, respectively, while E 0 and E + represent the energies of the neutral and cation species with the geometries of the cation and neutral species, respectively.
  • Hole Reorganization energies for embodiments may comprise from about 0 eV to about 0.5 eV. In some embodiments, the hole reorganization energy is from about 0.04 to about 0.35 eV. In some embodiments, the hole reorganization energy is 0.35 eV or less.
  • the hole reorganization energy is about 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.17, 0.19, 0.20, 0.22, 0.25, 0.27, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.37, 0.40, 0.45, or 0.50.
  • compositions described herein can be used to make a wide variety of devices.
  • the device can be a fused thiophene moiety-containing composition configured in an electronic, optoelectronic, or nonlinear optical device.
  • the compositions described herein can also be used in field effect transistors (FETs), thin-film transistors (TFTs), organic light-emitting diodes (OLEDs), PLED applications, electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, as non-linear optical (NLO) materials, as RFID tags, as electroluminescent devices in flat panel displays, in photovoltaic devices, and as chemical or biological sensors.
  • FETs field effect transistors
  • TFTs thin-film transistors
  • OLEDs organic light-emitting diodes
  • PLED applications electro-optic (EO) applications
  • conductive materials as two photon mixing materials
  • organic semiconductors as non-linear optical (NLO) materials
  • RFID tags as electrolumin
  • the polymers embodied herein are easier to modify on the designed fused rings, allowing for improvements in the polymerization process and processibility. Further, substituents can be introduced to multiple positions which can enable fine tuning material packing behaviors. The introduction of substituted pyrrole structures into substituted naphthalene results in lower reorganization energy and higher mobility for the compounds and finally ⁇ -substituents on the five-member ring increases the material stability of the resulting polymers.
  • N-BuLi 140 mL of 2.5 M solution
  • a solution of 2,6-bis(methoxymethoxy)-l,5-dimethylnaphthalene 29 g
  • anhydrous ethyl ether Et 2 0, 1 L
  • the solution was cooled to 0°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Electroluminescent Light Sources (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Described herein are heterocyclic organic compounds. More specifically, described herein are fused heterocyclic naphthalene compounds, polymers based on fused heterocyclic naphthalene compounds, methods for making these compounds, and uses thereof. The compounds described have improved polymerization and stability properties that allow for improved material processibility.

Description

NOVEL FUSED NAPHTHALENE CYCLOHETERO RING COMPOUNDS, AND METHODS AND USES THEREOF
Cross-reference to Related Applications
[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Serial No. 61/617,202 filed on March 29, 2012 the content of which is relied upon and incorporated herein by reference in its entirety.
Field
[0002] Described herein are compositions including heterocyclic organic compounds. More specifically, described herein are fused heterocyclic naphthalene compounds, methods for making them, and uses thereof.
Technical Background
[0003] Highly conjugated organic materials, due to their interesting electronic and optoelectronic properties, are being investigated for use in a variety of applications, including organic semiconductors (OSCs), field effect transistors (FETs), thin-film transistors (TFTs), organic light-emitting diodes (OLEDs), electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, and as non- linear optical (NLO) materials.
[0004] In particular, OSCs have attracted a great amount of attentions in the research community due to their advantages over inorganic semiconductors such as processing in any form, exhibiting a high mechanical flexibility, producing at low cost, and having a low weight. Polycyclic aromatic compounds, such as oligothiophenes, acenes, rylenes, phthalocyanens, and polythiophene, have been widely studied as semiconductor materials.
[0005] Among the organic p-type semiconductors, pentacene exhibits charge mobilities well above 1 cm2/V-s in organic field effect transistor devices. This number has been set up as a bench mark for new small molecule systems in terms of mobility requirements. However, due to the continuing need for improved performance and stability in semiconductor structures, there is an unmet need to develop better performing OSCs that have improved mobility, are structurally stable, and applicable to the large number of potential applications seen in the various high technology markets. Summary
[0006] Embodiments comprise a rationally designed a family of alkyl-substituted fused naphthalene hetero ring materials. The materials have several advantages in that it is easier to introduce substituents onto the fused rings allowing for significant improvement of the polymerization process and the polymer material processibility; substituents can be introduced to multiple positions which allows for fine tuning material packing behaviors; introduction of substituted pyrrole structures into the substituted naphthalene results in lower reorganization energy and higher mobility; and introduction of β-substituents on five member ring increases the material stability.
[0007] A first embodiment comprises a compound of formula:
Figure imgf000004_0001
Figure imgf000004_0002
Figure imgf000004_0003
Figure imgf000004_0004
Figure imgf000005_0001
wherein each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; y is H, halo, trialkylsilane, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs; and each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
[0008] In some embodiments, the compound is la or lb. In other embodiments, the compound is 2a, 2b, or 2c. In some embodiments, Xi is NRi, PRi, AsRi, Sb, O, S, Se, or Te; X2 is N or CRi; y is H, halo, optionally substituted C1-C40 alkyl, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, halo, OSO-alkyl, Mg- halo, Zn-halo, Sn(alkyl)3, B(OH)2, or B(alkoxy)2; and each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
[0009] In other embodiments, each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2- C40 alkenyl, optionally substituted C2-C40 alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, optionally substituted heterocyclyl, or an optionally substituted aryl or optionally substituted heteroaryl from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or naphthyridinyl.
[0010] In some embodiments, for 2a, 2b, or 2c, each Xi is independently NRi, PRi, AsRi, Sb, O, or Te or Se and each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, Xi and X2 may be bonded to one or more additional RiS. In other embodiments, for 2a, 2b, or 2c, each Xi is independently NRi, PRi, AsRi, Sb, O, S, Se, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri and each X2 is independently N, P, As, or SiRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri. In some embodiments, each X2 is independently N or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri .
[0011] In some embodiments, the compound comprises la, lb, 2a, 2b, or 2c, and the hole reorganization energy is less than 0.35 eV. In some embodiments, the hole reorganization energy is from about 0.05 to about 0.35 eV.
[0012] Another embodiment comprises a polymer of formula:
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000007_0003
Figure imgf000007_0004
Figure imgf000007_0005
wherein n is an integer greater than zero; k is from 1 to 10; m is from 0 to 10; with the proviso that when m is 0, k is null; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri ; y is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, hetero aryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs; each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, hetero aryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; and comonomer comprises an optionally substituted C2-C4o conjugated alkenyl, optionally substituted C2-C4o conjugated cycloalkenyl, optionally substitute C2-C4o conjugated hetero alkenyl, optionally substituted conjugated C2-C4o hetero cycloalkenyl, optionally substituted C6-C40 aryl, optionally substituted C6-C40 heteroaryl, or:
Figure imgf000009_0001
Figure imgf000009_0002
wherein m is 1, 2, or 3; o is 0, 1, 2, or 3; Rci, Rc2, Rc3, and are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
[0013] In some embodiments, Rci , R^, Rc3, and Rc4 are independently H, optionally substituted Ci-C4o alkyl, C2-C4o optionally substituted alkenyl, optionally substituted C2-C4o alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or optionally substituted phenyl, optionally substituted thiophenyl, optionally substituted furanyl, optionally substituted pyrrolyl, optionally substituted imidazolyl, optionally substituted triazolyl, optionally substituted oxaxolyl, optionally substituted thiazolyl, optionally substituted naphthalenyl, optionally substituted isoquinolinyl, optionally substituted quinolinyl, or optionally substituted naphthyridinyl.
[0014] In some embodiments, for la', lb', 2a', 2b', 2c', or 2d', Xi is NRh PRh AsRi, Sb, O, S, Se, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; X2 is N or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; y is H, halo, optionally substituted Ci-C4o alkyl, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, halo, OSO- alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, or B(alkoxy)2; and each Ri is independently H, halo, optionally substituted Ci-C4o alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone. In other embodiments, each Ri is independently H, halo, optionally substituted Ci-C4o alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, optionally substituted heterocyclyl, or an optionally substituted aryl or optionally substituted heteroaryl from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or naphthyridinyl. [0015] In some embodiments, for la', lb', 2a', 2b', 2c', or 2d', n is from 1 to 500; k is from 1-10; and m is from 0-10; with the proviso that if m is 0, then k is null. In some embodiments, the ratio of compound la, lb, 2a, 2b, or 2c to comonomer is from about 10: 1 to 1 : 10.
[0016] Another embodiment comprises a method of synthesizing a compound comprising:
Figure imgf000011_0001
comprising respectively allowing a compound of structure:
Figure imgf000011_0002
Figure imgf000012_0001
to undergo a substation reaction; wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, or Se; and each Z is independently Zi or I, each Zi is independently CI or Br, y is H, halo, trialkylsilane optionally substituted Ci- C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs. [0017] Another embodiment comprises a method of making a compound of structure:
Figure imgf000013_0001
comprising respectively allowing a compound of structure:
Figure imgf000013_0002
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000015_0001
undergo a ring cyclization reaction; wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; and each Z is independently Zi or I, each Zi is independently CI or Br.
[0018] Another embodiment comprises a method of making a compound of structure:
Figure imgf000015_0002
Figure imgf000016_0001
comprising respectively allowing a compound of structure
Figure imgf000016_0002
undergo a substitution reaction, wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each Z is independently Zi or I, each Zi is independently CI or Br; and each y is H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO- alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
[0019] Another embodiment comprises a method of making a polymer of structure:
Figure imgf000017_0001
Figure imgf000018_0001

Figure imgf000019_0001
with a compound of structure
Figure imgf000019_0002
wherein each y is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf; each u is independently H, halo, OSO-alkyl, Mg- halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf; each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, hetero aryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero ary It hiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; wherein comonomer comprises an optionally substituted C2-C40 conjugated alkenyl, optionally substituted C2-C40 conjugated cycloalkenyl, optionally substitute C2-C40 conjugated hetero alkenyl, optionally substituted conjugated C2-C40 heterocycloalkenyl, optionally substituted C6-C40 aryl, optionally substituted C6-C40 heteroaryl, or:
Figure imgf000020_0001
Figure imgf000020_0002
wherein each m is independently 1 , 2, or 3; o is 0, 1 , 2, or 3; u is Rci, R^, Rc3, and Rc4 are independently H, halo, optionally substituted Ci-C4o alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
[0020] Another embodiment comprises a device comprising compound la, lb, 2a, 2b, or 2c. Another embodiment comprises a device comprising polymer la', lb', 2a', 2b', 2c' or 2d'.
[0021] Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the embodiments as described in the written description and claims hereof, as well as in the appended drawings.
[0022] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework for understanding.
Brief Description of the Drawings
[0023] The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification.
[0024] FIG. 1 shows the importance the reorganization energy (R.E.) and the transfer integral in the charge carrier mobility (M). Based on the various plots shown for transfer integrals from 0.4 to 2.0 eV, it is clear that large increases in the transfer integral do not yield significant variation in the mobility, unless the reorganization energies are small.
[0025] FIG. 2 is a schematic diagram showing the internal reorganization energy (E) as a function of nuclear configuration (N.C.) for hole transfer from the neutral ground state (100) to a cationic state (200). The figure shows that E varies as a function of various internal reorganization components, λ = λ0+ , and the ionization potential
(l.?.), IP = E+ * -E .
Detailed Description
[0026] Before the present materials, articles, and/or methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific compounds, synthetic methods, or uses as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. [0027] In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings:
[0028] Throughout this specification, unless the context requires otherwise, the word
"comprise," or variations such as "comprises" or "comprising," will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
[0029] It must be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a pharmaceutical carrier" includes mixtures of two or more such carriers, and the like.
[0030] "Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.
[0031] Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
[0032] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.
[0033] The term "alkyl" refers to a monoradical branched or unbranched saturated hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. This term is exemplified by groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-hexyl, n-decyl, tetradecyl, and the like.
[0034] The term "substituted alkyl" refers to: (1) an alkyl group as defined above, having 1, 2, 3, 4 or 5 substituents, typically 1 to 3 substituents, selected from the group consisting of alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, amino carbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO- alkyl, -SO-aryl, -SO-heteroaryl, -S02-alkyl, S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and - S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkyl group as defined above that is interrupted by 1-10 atoms independently chosen from oxygen, sulfur and NRa, where Ra is chosen from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl and heterocyclyl. All substituents may be optionally further substituted by alkyl, alkoxy, halogen, CF3, amino, substituted amino, cyano, or -S(0)nRso, in which RSo is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (3) an alkyl group as defined above that has both 1, 2, 3, 4 or 5 substituents as defined above and is also interrupted by 1-10 atoms as defined above.
[0035] The term "alkylene" refers to a diradical of a branched or unbranched saturated hydrocarbon chain, having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, typically 1-10 carbon atoms, more typically 1, 2, 3, 4, 5 or 6 carbon atoms. This term is exemplified by groups such as methylene (-CH2-), ethylene (-CH2CH2-), the propylene isomers (e.g., -CH2CH2CH2- and -CH(CH3)CH2-) and the like.
[0036] The term "substituted alkylene" refers to: (1) an alkylene group as defined above having 1, 2, 3, 4, or 5 substituents selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, amino carbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -S02-alkyl, -S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1 , 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkylene group as defined above that is interrupted by 1-20 atoms independently chosen from oxygen, sulfur and NRa-, where Ra is chosen from hydrogen, optionally substituted alkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl and heterocyclyl, or groups selected from carbonyl, carboxyester, carboxyamide and sulfonyl; or (3) an alkylene group as defined above that has both 1, 2, 3, 4 or 5 substituents as defined above and is also interrupted by 1-20 atoms as defined above. Examples of substituted alkylenes are chloromethylene (- CH(C1)-), aminoethylene (-CH(NH2)CH2-), methylamino ethylene (-CH(NHMe)CH2- ), 2-carboxypropylene isomers (-CH2CH(C02H)CH2-), ethoxyethyl (-CH2CH20- CH2CH2-), ethylmethylaminoethyl (-CH2CH2N(CH3)CH2CH2-), and the like.
[0037] The term "aralkyl" refers to an aryl group covalently linked to an alkylene group, where aryl and alkylene are defined herein. "Optionally substituted aralkyl" refers to an optionally substituted aryl group covalently linked to an optionally substituted alkylene group. Such aralkyl groups are exemplified by benzyl, phenylethyl, 3-(4-methoxyphenyl)propyl, and the like.
[0038] The term "alkoxy" refers to the group R-0-, where R is an optionally substituted alkyl or optionally substituted cycloalkyl, or R is a group -Y-Z, in which Y is optionally substituted alkylene and Z is optionally substituted alkenyl, optionally substituted alkynyl; or optionally substituted cycloalkenyl, where alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl are as defined herein. Typical alkoxy groups are optionally substituted alkyl-O- and include, by way of example, methoxy, ethoxy, n- propoxy, iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2- dimethylbutoxy, trifiuoromethoxy, and the like.
[0039] The term "alkylthio" refers to the group Rs-S-, where Rs is as defined for alkoxy.
[0040] The term "alkenyl" refers to a monoradical of a branched or unbranched unsaturated hydrocarbon group typically having from 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms and even more typically 2 to 6 carbon atoms and having 1-6, typically 1, double bond (vinyl). Typical alkenyl groups include ethenyl or vinyl (- CH=CH2), 1 -propylene or allyl (-CH2CH=CH2), isopropylene (-C(CH3)=CH2), bicyclo[2.2.1]heptene, and the like. In the event that alkenyl is attached to nitrogen, the double bond cannot be alpha to the nitrogen.
[0041] The term "substituted alkenyl" refers to an alkenyl group as defined above having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -S02-alkyl, S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0042] The term "alkynyl" refers to a monoradical of an unsaturated hydrocarbon, typically having from 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms and even more typically 2 to 6 carbon atoms and having at least 1 and typically from 1-6 sites of acetylene (triple bond) unsaturation. Typical alkynyl groups include ethynyl, (- C≡CH), propargyl (or prop-l-yn-3-yl, -CH2C≡CH), and the like. In the event that alkynyl is attached to nitrogen, the triple bond cannot be alpha to the nitrogen.
[0043] The term "substituted alkynyl" refers to an alkynyl group as defined above having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -S02-alkyl, S02-aryl and - S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0044] The term "aminocarbonyl" refers to the group -C(0)NRNRN where each R is independently hydrogen, alkyl, aryl, heteroaryl, heterocyclyl or where both RN groups are joined to form a heterocyclic group (e.g., morpholino). Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0045] The term "acylamino" refers to the group -NRNCOC(0)R where each RNCO is independently hydrogen, alkyl, aryl, heteroaryl, or heterocyclyl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0046] The term "acyloxy" refers to the groups -0(0)C-alkyl, -0(0)C-cycloalkyl, - 0(0)C-aryl, -0(0)C-heteroaryl, and -0(0)C-heterocyclyl. Unless otherwise constrained by the definition, all substituents may be optionally further substituted by alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0047] The term "aryl" refers to an aromatic carbocyclic group of 6 to 20 carbon atoms having a single ring (e.g., phenyl) or multiple rings (e.g., biphenyl), or multiple condensed (fused) rings (e.g., naphthyl or anthryl). Typical aryls include phenyl, naphthyl and the like.
[0048] Unless otherwise constrained by the definition for the aryl substituent, such aryl groups can optionally be substituted with from 1 to 5 substituents, typically 1 to 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO- heteroaryl, -S02-alkyl, S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0049] The term "aryloxy" refers to the group aryl-O- wherein the aryl group is as defined above, and includes optionally substituted aryl groups as also defined above. The term "arylthio" refers to the group aryl-S-, where aryl is as defined as above.
[0050] The term "amino" refers to the group -NH2.
[0051] The term "substituted amino" refers to the group -NRWRW where each Rw is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, carboxyalkyl (for example, benzyloxycarbonyl), aryl, heteroaryl and heterocyclyl provided that both Rw groups are not hydrogen, or a group -Y-Z, in which Y is optionally substituted alkylene and Z is alkenyl, cycloalkenyl, or alkynyl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, amino carbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and - S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0052] The term "carboxyalkyl" refers to the groups -C(0)0-alkyl or -C(0)0- cycloalkyl, where alkyl and cycloalkyl, are as defined herein, and may be optionally further substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, in which RSo is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0053] The term "cycloalkyl" refers to carbocyclic groups of from 3 to 20 carbon atoms having a single cyclic ring or multiple condensed rings. Such cycloalkyl groups include, by way of example, single ring structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and the like, or multiple ring structures such as adamantanyl, bicyclo [2.2.1] heptane, l,3,3-trimethylbicyclo[2.2.1]hept-2-yl, (2,3,3- trimethylbicyclo[2.2.1]hept-2-yl), or carbocyclic groups to which is fused an aryl group, for example indane, and the like.
[0054] The term "cycloalkenyl" refers to carbocyclic groups of from 3 to 20 carbon atoms having a single cyclic ring or multiple condensed rings with at least one double bond in the ring structure.
[0055] The terms "substituted cycloalkyl" or "substituted cycloalkenyl" refer to cycloalkyl or cycloalkenyl groups having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO- heteroaryl, -S02-alkyl, S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0056] The term "halogen" or "halo" refers to fluoro, bromo, chloro, and iodo. [0057] The term "acyl" denotes a group -C(0)Rco, in which Rco is hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl.
[0058] The term "heteroaryl" refers to a radical derived from an aromatic cyclic group (i.e., fully unsaturated) having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms and 1, 2, 3 or 4 heteroatoms selected from oxygen, nitrogen and sulfur within at least one ring. Such heteroaryl groups can have a single ring (e.g., pyridyl or furyl) or multiple condensed rings (e.g., indolizinyl, benzothiazolyl, or benzothienyl). Examples of heteroaryls include, but are not limited to, [l,2,4]oxadiazole, [l,3,4]oxadiazole, [l ,2,4]thiadiazole, [l,3,4]thiadiazole, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, isoquinoline, quinoline, phthalazine, naphthylpyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, phenanthroline, isothiazole, phenazine, isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline, triazole, oxazole, thiazole, naphthyridine, and the like as well as N-oxide and N-alkoxy derivatives of nitrogen containing heteroaryl compounds, for example pyridine-N-oxide derivatives.
[0059] Unless otherwise constrained by the definition for the heteroaryl substituent, such heteroaryl groups can be optionally substituted with 1 to 5 substituents, typically 1 to 3 substituents selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO- heteroaryl, -S02-alkyl, S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0060] The term "heteroaralkyl" refers to a heteroaryl group covalently linked to an alkylene group, where heteroaryl and alkylene are defined herein. "Optionally substituted heteroaralkyl" refers to an optionally substituted heteroaryl group covalently linked to an optionally substituted alkylene group. Such heteroaralkyl groups are exemplified by 3-pyridylmethyl, quinolin-8-ylethyl, 4-methoxythiazol-2-ylpropyl, and the like.
[0061] The term " hetero aryloxy" refers to the group heteroaryl-O-.
[0062] The term "heterocyclyl" refers to a monoradical saturated or partially unsaturated group having a single ring or multiple condensed rings, having from 1 to 40 carbon atoms and from 1 to 10 hetero atoms, typically 1, 2, 3 or 4 heteroatoms, selected from nitrogen, sulfur, phosphorus, and/or oxygen within the ring. Heterocyclic groups can have a single ring or multiple condensed rings, and include tetrahydrofuranyl, morpholino, piperidinyl, piperazino, dihydropyridino, and the like.
[0063] Unless otherwise constrained by the definition for the heterocyclyl substituent, such heterocyclyl groups can be optionally substituted with 1, 2, 3, 4 or 5, and typically 1, 2 or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, amino carbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, hetero arylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, amino carbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO- heteroaryl, -S02-alkyl, -S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0)nRso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0064] The term "thiol" refers to the group -SH.
[0065] The term "substituted alkylthio" refers to the group -S-substituted alkyl.
[0066] The term "heteroarylthiol" refers to the group -S-heteroaryl wherein the heteroaryl group is as defined above including optionally substituted heteroaryl groups as also defined above.
[0067] The term "sulfoxide" refers to a group -S(0)Rso, in which RSo is alkyl, aryl, or heteroaryl. "Substituted sulfoxide" refers to a group -S(0)Rso, in which RSo is substituted alkyl, substituted aryl, or substituted heteroaryl, as defined herein.
[0068] The term "sulfone" refers to a group -S(0)2Rso, in which RSo is alkyl, aryl, or heteroaryl. "Substituted sulfone" refers to a group - S(0)2Rso, in which RSo is substituted alkyl, substituted aryl, or substituted heteroaryl, as defined herein.
[0069] The term "keto" refers to a group -C(O)-. [0070] The term "thiocarbonyl" refers to a group -C(S)-.
[0071] The term "carboxy" refers to a group -C(0)OH.
[0072] The term "conjugated group" is defined as a linear, branched or cyclic group, or combination thereof, in which p-orbitals of the atoms within the group are connected via delocalization of electrons and wherein the structure can be described as containing alternating single and double or triple bonds and may further contain lone pairs, radicals, or carbenium ions. Conjugated cyclic groups may comprise both aromatic and non-aromatic groups, and may comprise polycyclic or heterocyclic groups, such as diketopyrrolopyrrole. Ideally, conjugated groups are bound in such a way as to continue the conjugation between the thiophene moieties they connect.
[0073] Disclosed are compounds, compositions, and components that can be used for, can be used in conjunction with, can be used in preparation for, or are products of the disclosed methods and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated. Thus, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
[0074] Embodiments comprise a rationally designed a family of alkyl-substituted fused naphthalene hetero ring materials. The materials have several advantages in that it is easier to introduce substituents onto the fused rings allowing for significant improvement of the polymerization process and the polymer material processibility; substituents can be introduced to multiple positions which allows for fine tuning material packing behaviors; introduction of substituted pyrrole structures into the substituted naphthalene results in lower reorganization energy and higher mobility; and introduction of β-substituents on five member ring increases the material stability.
[0075] In one aspect, described herein are compositions comprising the formula la, lb, 2a, 2b, or 2c:
Figure imgf000031_0001
Figure imgf000031_0002
Figure imgf000031_0003
Figure imgf000031_0004
Figure imgf000031_0005
wherein each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; y is H, halo, trialkylsilane, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
[0076] Each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
[0077] In some embodiments, y is H, halo, -OSO-alkyl, -Mg-halo, -Zn-halo, - Sn(alkyl)3, -B(OH)2, or -B(alkoxy)2. In some embodiments, each Ri is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or aralkyl. In some embodiments, each Ri is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or optionally substituted phenyl, optionally substituted thiophenyl, optionally substituted furanyl, optionally substituted pyrrolyl, optionally substituted imidazolyl, optionally substituted triazolyl, optionally substituted oxaxolyl, optionally substituted thiazolyl, optionally substituted napthalenyl, optionally substituted isoquinolinyl, optionally substituted quinolinyl, or optionally substituted naphthyridinyl.
[0078] In some embodiments, for 2a, 2b, or 2c, each Xi is independently NRi, PRi, AsRi, Sb, O, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; and each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri. In other embodiments, for 2a, 2b, or 2c, each Xi is independently NRi, PRi, AsRi, Sb, O, S, Se, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri and each X2 is independently N, P, As, or SiRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri .
[0079] In another aspect, the composition comprises formula la', lb', 2a', 2b', 2c', or 2d':
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000033_0003
Figure imgf000033_0004
Figure imgf000034_0001
Figure imgf000034_0002
wherein n is an integer greater than zero; Xi, X2, y, and Ri all have the same meanings as above; k is from 1 to 10 with the proviso that when m is 0 (meaning no comonomer is present), k is null (meaning that the "k" term vanishes as it would become equivalent to the "n" term - therefore the polymer comprises "n" fused heterocyclic naphthalene groups as described by la', lb', 2a', 2b', 2c', or 2d'); m is from 0 to 10; the ratio of k to m may be from 1 : 10 to 10: 1 with the exception that when m is 0 the ratio of k to m is null; and n is from about 1 to 500. In some embodiments, k is 1 , 2 or 3. In some embodiments, m is 1 , 2, or 3. In some embodiments, the ratio of k to m is from about 3 : 1 to about 1 :3. In some embodiments, n is from about 3 to about 20, about 3 to about 15, about 3 to about 12, about 3 to about 10, or about 5 to about 9. In some embodiments, n is about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, or 500.
[0080] Comonomer, as used herein, describes a conjugated system such as any aromatic structure, double or triple bonds, or conjugated structures. Examples of comonomers include, but are not limited to:
Figure imgf000035_0001
Figure imgf000035_0002
wherein each m is independently is 1, 2, or 3; o is 0, 1, 2, or 3; Rd, Rc2, Rc3, and Rc4 are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone. In some embodiments, Rci , Rc2, Rc3, and Rc4 are independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or aralkyl. In some embodiments, Rci , Rc2, Rc3, and Rc4 are independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or optionally substituted phenyl, optionally substituted thiophenyl, optionally substituted furanyl, optionally substituted pyrrolyl, optionally substituted imidazolyl, optionally substituted triazolyl, optionally substituted oxaxolyl, optionally substituted thiazolyl, optionally substituted napthalenyl, optionally substituted isoquinolinyl, optionally substituted quinolinyl, or optionally substituted naphthyridinyl.
[0081] In another aspect, embodiments may be produced through a series of synthetic steps. For illustrative purposes, reaction Schemes 1-7 depicted below provide potential routes for synthesizing the embodiments as well as key intermediates. The methods disclosed in the instant Schemes and Examples are intended for purposes of exemplifying only and are not to be construed as limitations thereon.
[0082] Those skilled in the art will appreciate that other synthetic routes may be used to synthesize the inventive compounds. Some aspects of some embodiments may be synthesized by synthetic routes that include processes analogous to those well-known in the chemical arts, particularly in light of the description contained herein. Although specific starting materials and reagents are depicted in the schemes and discussed below, other starting materials and reagents can be easily substituted to provide a variety of derivatives and/or reaction conditions. The starting materials are generally available from commercial sources, such as Aldrich Chemicals (Milwaukee, Wis.), or are readily prepared using methods well known to those skilled in the art (e.g., prepared by methods generally described in Louis F. Fieser and Mary Fieser, REAGENTS FOR ORGANIC SYNTHESIS, V. 1-19, Wiley, New York (1967-1999 ed.), or BEILSTEINS HANDBUCH DER ORGANISCHEN CHEMIE, 4, Aufl. ed. Springer- Verlag, Berlin, including supplements (also available via the Beilstein online database)). In addition, many of the compounds prepared by the methods described below can be further modified in light of this disclosure using conventional chemistry well known to those skilled in the art.
[0083] In another aspect, compounds comprising la, lb, 2a, 2b, or 2c and intermediates leading to la, lb, 2a, 2b, or 2c may be synthesized. Scheme 1 exemplifies one possible synthetic routes for forming embodied compounds la and lb:
Scheme 1
Figure imgf000037_0001
wherein y, Xi and Ri have the same meanings as above (X2 is shown as -CH, but could be generalized to any X2), PG represents a protecting group, such as Me, MOM (methoxymethyl), EOM (ethoxymethyl), MTM (methylthiomethoxy), THP (tetrahydropyranyl), etc., each Z is independently Z\ or I, each Z\ is independently CI or Br, each S02Rx is independently S02(CF2)xF , wherein x is from 1-20, Ts, or Ms.
[0084] As noted in Scheme 1 , a naphthalene diol compound, (1), may be reacted with N-bromosuccinimide in THF at a 1 :2 ratio, and quenched with saturated sodium thiosulfate to produce l,5-dibromonaphthalene-2,6-diol, (2). Compound (2) may be reacted with an alcohol protecting group, such as excess chloro(methoxy)methane in dichloromethane and diisopropylethylamine, and quenched with water after 22 hours. After extraction, l-5-dibromo-2,6-bis(PG)naphthalene, (3), may be obtained. Compounds of form (3) may be combined with n-butyl lithium (2.4 equiv) in an organic solvent, then combined with a halo-alkyl, such as iodomethane, in THF, extracted with saturated sodium sulfate, washed, dried, and purified to give 3,7,- dibromo-2,6-bis(PG)-l,5-dialkylnaphthalene, compound (4).
[0085] Compounds of form (5) may be formed via halogenation of compound (4). The general reaction for iodination is shown below and is very similar to bromination of (4), except that I2
Figure imgf000038_0001
For example, compound (4) may be combined with n-BuLi (2.4 eq.) in solvent (e.g., anhydrous ethyl ether) at room temperature. After sufficient time, the solution can be cooled to 0°C and a THF solution of diiodine (I2) added. The resulting mixture is allowed to warm to room temperature over time, quenched, and the aqueous layer extracted. The combined organic extracts can be washed and dried to give compound (5) ((5b) in the case of diiodine). After evaporation, the resulting crude product can be purified by column chromatography on silica gel.
[0086] Compounds of structure (6), 3,7-dihalo-l,5-dialkylnaphthalene-2,6-diol, may be produced from compound (5) by combining (5) with 6N HCl in dichloromethane/methanol (1 : 18 ratio), heating, stirring overnight, pouring into water, and extracting with ethyl acetate.
[0087] Compounds of structure (7a), 3,7-Dihalo-l ,5-dialkylnaphthalene-2,6-diyl bis(trifluoromethanesulfonate), may be formed by reaction of compound (6) in an organic solvent, such as pyridine and dichloromethane, with trifluoromethanesulfonic anhydride (1 :2), mixed with water and 1M HCl, extracted with dichloromethane and concentrated in vacuo. The residue may then be purified to give compound (7a) at about 80% yield.
[0088] Compounds (7b) may be formed from compounds (6) by adding Tetrakis(triphenylphosphine)palladium(0) ((Pd(PPh3)4), Cul, triethylamine, diisopropylamine and terminal alkynes to a degassed solution of (6), stirring at 80°C, and adding water and 1M HCl after approximately 15 minutes. The resulting mixture can be extracted and the combined organic layers dried and concentrated to give (7b) (see, e.g., Zhao,Y.; et al. 15 CHEM. EUR. J. 13356 (2009)), incorporated by reference in its entirety).
[0089] Compounds (8a) may be formed from compounds (7a) by adding bis(triphenyphosphine) palladium chloride ((Pd(PPh3)2Cl2), Cul, and terminal alkynes to a degassed solution of (7a) in solvent (e.g., THF or DMF), stirring at room temperature, and adding water and 1M HCl after approximately 1 hour. The resulting mixture can be extracted and the combined organic layers dried and concentrated to give (8a) (see, e.g. Shinamura, S. et al. 133 J. AM. CHEM. SOC. 5024 (2011), incorporated by reference in its entirety).
[0090] Compounds of structures (8b) may be formed by reaction of compound (7b) in an organic solvent, such as pyridine and dichloromethane, with trifluoromethanesulfonic anhydride (1 :2), mixed with water and 1M HCl, extracted with dichloromethane and concentrated in vacuo. The residue may then be purified to give compound (8b) (see, e.g. Shinamura, S. et al. 133 J. AM. CHEM. SOC. 5024 (2011), incorporated by reference in its entirety).
[0091] When
Figure imgf000039_0001
is Br, Compound (9a) may be formed from compound (8a) via reaction of (8a) with tBuONa, tris(dibenzylideneacetone)dipalladium(0), and 2,2'- bis(diphenylphosphino)-l, l'-binaphthyl in dry solvent. Primary amines may be added via a syringe and the mixture was refluxed under nitrogen for 4 h. After cooling to room temperature, water can be added to the solution and the reaction mixture extracted. After drying and solvent evaporation, the residue may be purified to give compound (9a) (see, e.g., Lu et al, 160 SY . METALS 1438-41 (2010), incorporated by reference in its entirety).
[0092] In the case wherein x is NHR and
Figure imgf000039_0002
is CI, compound (9a) may be formed from compound (8a) via combination with aryl chloride, amine, KOtBu and a catalyst in 1 ,2- dimethoxyethane. The mixture may be stirred at room temperature in an air atmosphere and monitored by GC/GC-MS. The reaction may be quenched with water, extracted with solvent, dried, concentrated and purified to give the desired product (see, e.g., Lee et al., 13 ORG. LETT. 5540 (2011), incorporated by reference in its entirety).
[0093] Compound (9b) may be formed from compound (8b) via reaction of (8b) with Cs2C03, Tris(dibenzylideneacetone)dipalladium(0), and 2,2'-bis(diphenylphosphino)- Ι,Γ-binaphthyl in dry solvent. Primary amines may be added via a syringe and the mixture was refluxed under nitrogen for 4 h. After cooling to room temperature, water can be added to the solution and the reaction mixture extracted. After drying and solvent evaporation, the residue may be purified to give compound (9b).
[0094] Alternatively, compound (9b) may be formed from compound (8b) via reaction of (8b) with Si(SH)(i-Pr)3 in solvent (Thompson et al, 21 BIOORG. MED. CHEM. LETT. 3764-66 (2011) , herein incorporated by reference), as noted below:
Figure imgf000040_0001
wherein R2 is an alkyl or aryl.
[0095] Compounds (10a) and (10b) may be formed from compounds (9a) and (9b), respectively, via a number of ring cyclization processes. The first comprises combining in a dried pressure tube either compound (9a) or (9b) in DMSO or an alternative solvent with finely crushed KOH. The resulting reaction mixture was heated at 120°C for 17 hours and was extracted with ethyl acetate, dried, concentrated and purified by column chromatography {see, e.g., Verma et al, 13 ORG. LETT. (2011), incorporated by reference in its entirety). The second comprises combining (9a) or (9b) with a ruthenium catalyst in dry/deoxygenated solvent (e.g., THF) in a scintillation vial under an inert atmosphere, such as in a glove box. The mixture can then be sealed and heated (~70°C) for an extended period of time (~2 days), while being monitored for completion of the reaction. The resulting products may be purified by column chromatography {see, e.g., Nair et al, 16 CHEM. EUR. J. 7992 (2010), incorporated by reference in its entirety). A third possible method involves (9a) or (9b) with triethylamine and Cul in a solvent (e.g., DMF) under an inert atmosphere (e.g., a Schlenk line). The flask may then be sealed and heated with reaction progress monitored by gas chromatography. The reaction products may be purified, for example, by adsorbing directly onto a Teledyne Isco silica load cartridge followed by elution onto a Teledyne Isco column using a 0 to 20% ethyl alcohol/hexane solution {see, e.g., Arnold et al, 13 ORG. LETT. 5576 (2011), incorporated by reference in its entirety). Another method of forming compounds (10a) and (10b) from compounds (9a) and (9b) comprises reacting (9b) or (9a) with NaOH in ethyl acetate and N-methylpyrrolidone at 5C, then allowing the reaction to warm to room temperature for 30 minutes (WO 2011147690, herein incorporated by reference in its entirety).
[0096] Alternatively, Compounds (10a) and (10b) may be formed from compounds (8a) and (8b), respectively, using a number of different methods. The first is the general cyclization procedure for dibromodiethynylnaphthalene analogues described in Shoji et al, 133 J. AMER. CHEM SOC. 5024-5035 (2011) (incorporated by reference in its entirety). The procedure combines Na2S in NMP with (8a) or (8b) and heating to about 185°C for about 12 hours, then adding the solution to a saturated aqueous ammonium chloride solution to precipitate. The precipitate is collected by filtration, washed, and purified by vacuum sublimation to give (10a) or (10b). Second, per Guilarte et al, 13 ORG. LETT. 5100-5103 (2011) (incorporated by reference in its entirety), a solution of (8a) or (8b) is combined with Pd2DBA3, LiHMDS, and 4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene (Xantphos) in dry solvent (e.g., toluene) and stirred under inert atmosphere for a short time (~2 min). Then TIPS-SH can be added and the mixture stirred at ~120°C until all aryl bromide is consumed as measured by GC-MS. After cooling, TBAF (3 equivalents) can be added to the mixture and the mixture is stirred for 2 hours. The resulting products may be extracted and purified by column chromatography. The third method is similar to the second, in that it combines a solution of (8a) or (8b) is combined with Pd2DBA3, LiHMDS, and 4,5- bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) in dry solvent (e.g., toluene) and stirred under inert atmosphere for a short time (~2 min), then addition of TIPS-SH. The resulting solution may be stirred under inert atmosphere in a microwave at 130°C and 300W until all aryl bromide is consumed as measured by GC-MS. Then Cs2C03 can be added to the mixture and microwave irradiation continued until the reaction is complete. The resulting products may be extracted and purified by column chromatography (Guilarte et al., 13 ORG. LETT. 5100-5103 (2011) (incorporated by reference in its entirety)).
[0097] Schemes 2 and 3 are synthetically similar to Scheme 1, but provide for the synthesis of the 2a, 2b, and 2c:
Scheme 2
Figure imgf000042_0001
Wherein Rl s y, Zl s Xi, and Rx are the same as described in Scheme 1 (X2 is shown as - CH, but could be generalized to any X2). The reaction schemes for Schemes 2 and 3 are somewhat simpler in that the hydroxide group does not need to be protected as no Ri group is being added as in Scheme 1. Production of compounds (7c)-(10c) and (7d)- (lOd) is done as noted above for (7a)-(10a). Compounds of structures (lOcl) and (lOdl), may be formed by reaction of compound (10c) and (lOd) respectively, n- Butyllithium in hexanes (Aldrich) was added dropwise to a solution of (10c) or (lOd) respectively in an organic solvent, such as tetrahydraiuran, may afford the lithiation product of (10c) or (lOd) respectively, which could be quenched with electrophilic reagents. After workup, the residue may then be purified to give either compound (lOcl) or compound (lOdl) (see, e.g. Katritzky, A. et al, 53 J. ORG. CHEM.794 (1988) ), incorporated by reference in its entirety).
[0098] In another aspect, compounds comprising la, lb, 2a, 2b, or 2c and polymer precursors may be produced through a series of synthetic steps. The embodiments are shown in Scheme 4 as products (llbl), (llb2), and (llb3) resulting from (10b):
Scheme 4
Figure imgf000043_0001
Wherein Ri and Xi are the same as described in Scheme 1 and R3 is alkyl (X2 is shown as -CH, but could be generalized to any X2). Similarly, polymer precursors (Hal), (Ha2), and (Ha3) may be obtained from (10a), (10c), and (lOd) with the appropriate chemical structure using the same synthetic procedures described below.
[0099] Possible routes from (10b) to (llbl) include the combination of (10b) (1.5 mmol) with NBS (3.6 mmol) in organic solvent (e.g., chloroform), stirring at room temperature for 24 hours, and subsequent washing (saturated sodium carbonate/water), extraction (DCM), drying with Na2S04, and purification (Huang et al., 13 ORG. LETT. 5252 (2011), incorporated by reference in its entirety) or combination of (10b) with slow addition of PyHBr3 (1 eq.) in solvent (THF/CHC13) and stirring for approx. 30 minutes at 0°C. The reaction is then diluted with dichloro methane and washed (2x100 mL Na2S203), washed with brine, dried over Na2S04, and purified by flash chromatography (gradient eluent 5% EtOAc/hexanes to 20% EtOAc/hexanes) (Qi et al., 133 J. AM. CHEM. SOC. 10050 (2011), incorporated by reference in its entirety, and Luo et al., 5 ORG. LETT.4709-12 (2003), incorporated by reference in its entirety).
[00100] One possible route from (10b) to (llb2) is the combination of (10b) (5.52 mmol) with n-butyllithium (13.84 mmol, 2.5 M in hexane, added dropwise) under inert atmosphere in dry solvent (e.g., 12 mL hexane) at low temperatures (-78°C), then allow to warm to room temperature, and subsequently cooled to -78°C after about 20 minutes. A solution of tributylstannyl chloride (16.62 mmol) may be added dropwise, and then the solution can be brought to room temperature and stirred overnight. The mixture is then washed and the product washed, dried, and purified via column chromatography (dichloro methane :hexane = 1 :20 (v:v) (containing small amount triethylamine)) (Peng et al., 23 ADV. MATER. 4554 (2011), incorporated by reference in its entirety). A second route from (10b) to (llb2) is the combination of(10b) (1 eq.) with n-butyllithium (dropwise addition, 2.5 eq.) in tetramethylpiperidine (2.3 eq.) and THF (20 mL) at -78°C, then addition of R3SnCl (3 eq.) at -78°C. The mixture may then be quenched with NaHC03, extracted with EtOAc, dried and purified by flash chromatography (Fargeas et al., 9 EUR. J. ORG. CHEM. 1711-21 (2003), incorporated by reference in its entirety).
[00101] A first route from (llbl) to (llb2) comprises combining (llbl) (0.80 mmol) with n-butyllithium (2 mmol) under inert atmosphere (argon) in dry solvent (THF) at low temperatures (-78°C), then allow to warm to room temperature, and subsequently cooled to -78°C after about 20 minutes. A solution of trimethylstannyl chloride (1.2 mmol 1.2 mL hexane) may be added dropwise, and then the solution can be brought to room temperature and stirred overnight. The mixture is then quenched with water, extracted with ether, dried, evacuated in vacuo, and recrystallized from isopropanol and hexanes (Peng et al., 23 ADV. MATER. 4554 (2011), incorporated by reference in its entirety). A second route from (llbl) to (llb2) comprises combining (llbl) with n-butyllithium (2.98 mmol) in l-tert-butyl-6-methyl-2-bromo-3- cyclohexyl-lH-indole-l,6-dicarboxylate (2.29 mmol) and THF (35 mL) at -78°C, then addition of R3SnCl (3.43 mmol) at -78°C, then allowing the mixture to warm to room temperature. The mixture may then be quenched with H20/NaHC03, extracted, dried and purified via flash chromatography (2:98 EtOAc/petroleum ether) (Avolio et al., 48 J. MED. CHEM. 4547 (2005), incorporated by reference in its entirety).
[00102] One possible route from (10b) to (llb3) is the combination of (10b) (3.24 mmol) with n-butyllithium (added dropwise, 2.88 mmol) in THF (35 mL) under inert atmosphere at room temperature and then stirred at ~50°C for 2 hours. Then 2- isopropoxy-4,4,5,5- tetramethyl-l,3,2-dioxaborolane (8.1 mmol) may be added in one portion at room temperature. After ~ 6 hours, the reaction is stopped and the organic layer extracted (diethyl ether) and purified by column chromatography (Huo et al., 49 A GEW CHEM. INT. ED. 1500 (2010), incorporated by reference in its entirety). A second route from (10b) to (llb3) is the combination of (1,5- cyclooctadiene)(methoxy)iridium(I) dimmer (0.15 eq.), 4,4'-di-tert-butyl-2,2'-dipyridyl (0.03 eq.), bis(pinacolato)diboron (2.00 eq.), 10b (1 eq.), and a stirring bar in a dry flask under argon. To this mixture is added anhydrous dichloromethane (2.2. mL) to give a colorless suspension and the flask is heated at 65°C. After ~3 hours, the mixture is cooled to 23°C and volatile removed under reduced pressure, and then the product is purified by flash chromatography (Schneider et al., 13 ORG. LETT. 3588 (2011) and Kolundzic et al, 133 J. AM. CHEM. SOC. 9104-11 (2011), both incorporated by reference).
[00103] Conversion from (llbl) to (llb3) may be accomplished by a number of routes. The first involves dissolving (llbl) (1.2 mmol) in anhydrous THF (25 mL) or an equivalent solvent and cooling to -78°C, then adding n-butyllithium (2.2. eq.) and stirring. Next, 2-isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (4 eq.) may be added and the reaction stirred overnight. The product is extracted, washed, filtered and the solvent evaporated to give an oil that may be purified via column chromatography (e.g., 12" silica column run with cyclohexane/ethyl acetate (4: 1)) (Brookins et al. 19 J. MATER. CHEM. 4197 (2009), incorporated by reference in its entirety). Alternatively, to a solution of (llbl) (5.0 mmol in 400 mL 1,4-dioxane) may be added pinacolborane (357 mmol), then triethylamine 476 (mmol) dropwise at room temperature. After stirring for ~3 hours, addition of (2-biphenyl)dicyclohexylphosphine (14.3 mmol) and Pd(OAc)2 (3.57 mmol) is done. The combined mixture is then heated to about 85°C for about 1.5 hours. Subsequently, a saturated aqueous NH4C1 solution is added to the mixture and the product extracted with EtOAc, washed, dried and filtered, and then triturated in hexane:EtOAc (20: 1) (Ikegashira et al. 49 J. MED. CHEM. 6950 (2006), incorporated by reference in its entirety).
[00104] In another aspect, compounds comprising la', lb', 2a', 2b', or 2c' may be produced through a series of synthetic steps. Compounds may be synthesized by synthetic routes that include processes analogous to those well-known in the chemical arts, particularly in light of the description contained herein. Scheme 5 exemplifies one way to form embodied compounds:
Scheme 5
Figure imgf000046_0001
wherein n, Xl s X2, y, Rl s n and comonomer all have the same meanings as above, k = m = 1, and each Q is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf Similarly, polymers comprising lb, 2a, 2b, or 2c may be made using the same synthetic procedures described herein. If the naphthalene reactant is (10a)-(10d), then (10a)-(10d) may be combined with dibromide comonomer (1 : 1 ratio), trans-di(μ-acetato)bis[o-(di-o-tolyl-phosphino)benzyl]dipalladium(II) (4% mol) and Cs2C03 (2 eq.) and placed in a microwave vial with a magnetic stirring bar. The vial is then sealed with a cap and purged with nitrogen to remove the oxygen. THF is added and the reaction is heated with an oil bath at 120°C (reaction under pressure). At the end of the reaction time, the reaction is cooled and the corresponding 5- alkyl[3,4-c]pyrrole-4,6-dione is added in excess as a capping agent. The solution was heated again at 120°C for 1 hour to complete the end-capping procedure. After cooling, the mixture is poured in to 500 mL of cold methanol to precipitate to product. The precipitate is filtered, extracted via Soxhlet extraction with acetone followed by hexanes to remove catalytic residue and low MW materials. Polymers may be extracted with chloroform and then re -precipitated by re-pouring into cold methanol and filtering (Berrouard et al., 50 ANGEW. CHEM. INT. ED. 1-5 (2011), incorporated by reference in its entirety).
[00105] Alternatively, if the naphthalene reactant is (llbl) or (llal), the polymer may be formed by combining (llb2) (or (lla2)) (0.25 mmol) with ditin, or diboranes or diboronate esters (comonomer) (1 : 1 eq.) in toluene (15 mL). The solution is flushed with argon for 10 min, and then Pd2DBA3 (2 mol%) and P(o-tolyl)3 (16.36 mg, 8%) are added into the flask. The flask is purged, heated to 110°C, and stirred for 48 h under argon. 2-Tributylstannyl thiophene (20 μί) is then added to the reaction and after two hours, 2-bromothiophene (6.3 μί) is added and the mixture is stirred overnight to complete the end-capping reaction. The mixture is then cooled to room temperature, and the product filtered, washed with methanol (350 mL) and hexane in a Soxhlet apparatus to remove the oligomers and catalyst residue. Finally, the polymer is extracted with chloroform, condensed by evaporation and precipitated into methanol. The polymer was collected as a dark purple solid (Peng et al., 23 ADV. MATER. 4554 (2011), incorporated by reference in its entirety and Huo et al., 49 ANGEW CHEM. INT. ED. 1500 (2010), incorporated by reference in its entirety).
[00106] A second alternative for Scheme 5 is to start with (llb2) or (lla2). For example, (llb2) (0.25 mmol) and the dibromide comonomer (1 : 1 eq.) are dissolved in toluene (15 mL). The solution is flushed with argon for 10 min, and then Pd2DBA3 (2 mol%) and P(o-tolyl)3 (16.36 mg, 8%) are added into the flask. The flask is purged, heated to 110°C, and stirred for 48 h under argon. 2-Tributylstannyl thiophene (20 μί) is then added to the reaction and after two hours, 2-bromo thiophene (6.3 μί) is added and the mixture is stirred overnight to complete the end-capping reaction. The mixture is then cooled to room temperature, and the product filtered, washed with methanol (350 mL) and hexane in a Soxhlet apparatus to remove the oligomers and catalyst residue. Finally, the polymer is extracted with chloroform, condensed by evaporation and precipitated into methanol. The polymer was collected as a dark purple solid (Peng et al., 23 ADV. MATER. 4554 (2011), incorporated by reference in its entirety).
[00107] A third alternative for Scheme 3 is to start with (llb3) or (lla3). For example, (llb3) (0.35 mmol) and dibromide comonomer (1 : 1 eq.) are dissolved in toluene (15 mL) with sodium carbonate (1M, 3 mL). The solution is flushed with argon for 10 min, and then Ρά(ΡΡ1¾)4 (15 mg) is added into the flask. The flask is purged, heated to 110°C, and stirred for 18 h under argon. The mixture is then cooled to room temperature, and the product filtered, washed with methanol (100 mL) and hexane in a Soxhlet apparatus to remove the oligomers and catalyst residue. Finally, the polymer is extracted with chloroform, condensed by evaporation and precipitated into methanol. The polymer was collected as a dark purple solid (Huo et al., 49 ANGEW CHEM. INT. ED. 1500 (2010), incorporated by reference in its entirety).
[00108] Scheme 6 exemplifies another possible way to form embodied compounds:
Scheme 6
Figure imgf000048_0001
wherein n, Xl s X2, y, Rl s n and comonomer all have the same meanings as above, and k > 1 and m > 1.
[00109] Starting with (llbl) or (llal), the polymer in Scheme 6 may be formed by combining (llbal) (or (llal), dibromide comonomer (1 : 1 eq.), zinc powder (3.1 eq.), triphenyl phosphine (1 eq.), bipyridine (0.075 eq.), and nickel (II) chloride (0.075 eq.) in a dry round bottom flask inside of a dry box. The flask is sealed with a septum and removed from the dry box and anhydrous DMAC is added via cannulation. The reaction is heated to 85°C and after about five minutes, the reaction has a green-yellow color, with the yellow growing in intensity overtime. The reaction may be run for 24 hours, and then the polymer is precipitated into methanol and dried under vacuum.
[00110] Scheme 7 exemplifies another possible way to form embodied compounds:
Scheme 7
Figure imgf000048_0002
(l lbl3)
Figure imgf000048_0003
wherein n, Xl s X2, y, Rl s n and comonomer all have the same meanings as above, and k > 1 and m > 1.
[00111] Starting with (llbl) or (llal), the polymer in Scheme 5 may be formed by first dissolving (llbl) (or (llal)) in anhydrous THF and then adding n-butyllithium (1.2 eq.) and stirring. 2-Isopropoxy-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (4 eq.) is added and the reaction stirred overnight. The product was extracted, washed, dried and evaporated give (llbl3), which can be purified via with cyclohexane/ethyl acetate (4: 1) column chromatography. Compound (llbl3) is combined with cesium fluoride (7 eq.) in a dry flask purged with argon and then the comonomer is added in degassed solvent (12 mL per mmol of monomer) along with Pd2dba3 (2 mol%) and tri(t- butyl)phosphonium tetrafluoroborate (6 mol%), and the reaction is refluxed for 48 h. The polymer is precipitated into methanol and dried under vacuum.
[00112] Comonomers may be produced by known synthetic methods. Such methods are shown in, for example, 72 J. ORG. CHEM. 442-451 (2007), 6 BEILSTEIN J. ORG. CHEM. 830-845 (2010), Jerry March, Michael B. Smith, MARCH'S ADVANCED ORGANIC CHEMISTRY: REACTIONS, MECHANISMS, AND STRUCTURE (6th Ed. Wiley- Interscience), Richard C. Larock, COMPREHENSIVE ORGANIC TRANSFORMATIONS (1999 Wiley-VCH), all hereby incorporated by reference in their entireties.
[00113] In another aspect, embodiments herein are optimized for reorganization energy and mobility. In some embodiments, compounds embodied herein have improved solid state properties as a result of lower reorganization energy and/or higher mobility. In some embodiments, the properties of the compounds embodied herein may be described by Marcus theory (R.A. Marcus, 65 REV. MOD. PHYS. 599 (1993), herein incorporated by reference in its entirety).
[00114] Charge transport properties depend critically on the degree of ordering of the system or molecular ordering in the solid state, as well as the density of chemical impurities and/or structural defects such as grain size and dislocations. At the electronic level, two of the most important factors that control transport properties in organic conjugated materials are the interchain transfer integral β, and the reorganization energy λ. The transfer integral expresses the ease of transfer of a charge between interacting chains. The reorganization energy term describes the strength of the electron-phonon coupling. It is proportional to the geometric relaxation energy of the charged molecule over the individual neutral unit. In the context of semi-classical electron-transfer theory, the electron-transfer (hopping) rate can be expressed from Marcus theory in a sim lified way as:
Figure imgf000049_0001
(R.A. Marcus, 65 REV. MOD. PHYS. 599 (1993), herein incorporated by reference in its entirety) where T is the temperature, λ is the reorganization energy, β is the transfer integral, and h and ks are the Planck and Boltzmann constants, respectively.
[00115] It is possible to simplify equation (1) to:
Figure imgf000050_0001
In order to characterize the relative influence of both parameters λ and β to the charge transport rate. Fig. 1 schematically depicts the relationship of mobility (M) as a function of the reorganization energy (R.E.) at five different values of the transfer integral (ranging from 0.4 eV to 2 eV). From Fig. 1, it is clear that the difference in mobility for different transfer integrals is only significant for small values of the reorganization energy. A big increase in the transfer integral does not yield a significant variation in the mobility, unless the reorganization energies are small. This implies that any optimization of the mobility should start with the design of single molecules with very low reorganization energy.
[00116] The reorganization energy includes two contributions that are associated with charge hopping. One is introduced by the geometric changes within the single molecule, and is denoted the internal part. The second one arises from the repolarization changes of the surrounding medium and is usually much smaller than the first one. In studies to qualitatively order molecules it is generally valid to neglect this last contribution in the evaluation of the reorganization energy as no significant solvent reorganization occurs during the charge transfer in the condensed phase.
[00117] Table 1 incorporates reorganization energies for a number of embodiments. For each molecule, the geometry is optimized using quantum mechanics for both neutral and ionic states. Consequently, the basic hopping step in a molecular wire is defined by four energies: E0 and E+ represent the energies of the neutral and cation species in their lowest energy geometries, respectively, while E0 and E+ represent the energies of the neutral and cation species with the geometries of the cation and neutral species, respectively.
[00118] The quantum mechanics calculations to determine these above mentioned quantities used the experimentally parameterized Hamiltonian PM6 implemented in VAMP® semi-empirical molecular orbital software (Accelrys Software Inc.). Pentacene was used as the reference to validate the Hole Reorganization Energy calculations. Experimental data for Pentacene RE was -0.12 eV {see M. Malagoli and J.L. Bredas, 327 CHEM. PHYS. LETT. 13 (2000) and N.W. Gruhn et al, 89 PHYS. REV. LETT. 275503 (2002), both hereby incorporated by reference in their entirety), compared to 0.114 eV from our calculations based on VAMP® (Accelrys Software Inc.). [00119] Hole Reorganization energies for embodiments may comprise from about 0 eV to about 0.5 eV. In some embodiments, the hole reorganization energy is from about 0.04 to about 0.35 eV. In some embodiments, the hole reorganization energy is 0.35 eV or less. In some embodiments, the hole reorganization energy is about 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.17, 0.19, 0.20, 0.22, 0.25, 0.27, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.37, 0.40, 0.45, or 0.50.
Figure imgf000051_0001
Figure imgf000052_0001
y s enzoc , , t a azoe Compound Vertical Vertical Hole
Ionization Electron Reorganization Potential Affinity Energy [eV] [eV] [eV]
6.80 -1.61 0.134 ,9-dimethyl-2,7-di(thiophen-2-yl)-l,6- dihydroindolo[6,5-fJindole
7.45 -1.59 0.139
5,10-dimethylnaphtho[2,3-b:6,7- b']dithiophene
7.39 -2.01 0.142
5,10-dimethyl-2,7-di(thiophen-2- yl)naphtho[2,3-b:6,7-b']dithiophene
7.35 -1.74 0.143
5 , 10- dimethyl-3 , 8 - di(thiophen-2- yl)naphtho[2,3-b:6,7-b']dithiophene
7.52 -2.55 0.158 ,4'-(5, 10-dimethylnaphtho[2,3-b :6,7- b']dithiophene-2,7- diyl)bis(benzo[c] [1 ,2,5]thiadiazole)
Figure imgf000054_0001
Figure imgf000055_0001
diyl)bis(benzo[c] [1 ,2,5]thiadiazole)
Figure imgf000056_0001
b]thieno[2,3-d]thiophene
[00120] The compositions described herein (monomers, oligomers, polymers) can be used to make a wide variety of devices. For example, the device can be a fused thiophene moiety-containing composition configured in an electronic, optoelectronic, or nonlinear optical device. The compositions described herein can also be used in field effect transistors (FETs), thin-film transistors (TFTs), organic light-emitting diodes (OLEDs), PLED applications, electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, as non-linear optical (NLO) materials, as RFID tags, as electroluminescent devices in flat panel displays, in photovoltaic devices, and as chemical or biological sensors.
[00121] The polymers comprising the fused thiophene moieties described herein
(la', lb', 2a', 2b', 2c', and 2d') possess several advantages over similar compounds. The polymers embodied herein are easier to modify on the designed fused rings, allowing for improvements in the polymerization process and processibility. Further, substituents can be introduced to multiple positions which can enable fine tuning material packing behaviors. The introduction of substituted pyrrole structures into substituted naphthalene results in lower reorganization energy and higher mobility for the compounds and finally β-substituents on the five-member ring increases the material stability of the resulting polymers.
Examples
[00122] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the materials, articles, and methods described and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Although specific starting materials and reagents are depicted in the Examples below, other starting materials and reagents can be easily substituted to provide a variety of derivatives and/or reaction conditions. In addition, many of the compounds prepared by the methods described below can be further modified in light of this disclosure using conventional chemistry well known to those skilled in the art. Only reasonable and routine experimentation will be required to optimize such process conditions.
Example 1 - l,5-dibromonaphthalene-2,6-diol
Figure imgf000057_0001
[00123] To a solution of naphthalene -2, 6-diol (1) (5.1 g) in 50 mL of
Tetrahydrofuran (THF), was added N-Bromosuccinimide (NBS, 1 1.4 g). The mixture was re fluxing and monitored by GCMS. The reaction was quenched with saturated sodium thiosulfate, and filtered. The solid was washed by water to afford 1 ,5- dibromonaphthalene-2,6-diol (90%). LRMS (ESI): Calcd. for Ci0H6Br2O2: 317.8714, Found: 317.9.
Example 2 - l,5-Dibromo-2,6-bis(methoxymethoxy)naphthalene
Figure imgf000057_0002
[00124] To a solution of l ,5-dibromonaphthalene-2, 6-diol (2) (77.15 g) in dichloromethane (500 mL), diisoprorylethylamine (255 mL) and chloro(methoxy)methane (MOMCl, 98.6 g) were added at 0°C. After stirring for 22 h at room temperature, the reaction was quenched by adding water. The crude products were extracted with ethyl acetate and the combined organic extracts were washed with brine, dried over sodium sulfate (Na2S04), and concentrated in vacuum. The solid residue was stirred in n-hexanes to afford analytically pure l ,5-dibromo-2,6- bis(methoxymethoxy)naphthalene (90%). LRMS (ESI): Calcd. for Ci4Hi4Br204: 405.9238, Found: 406.0.
Example 3 - 2,6-bis(methoxymethoxy)-l,5-dimethylnaphthalene
Figure imgf000058_0001
[00125] l,5-dibromo-2,6-bis(methoxymethoxy)naphthalene (100 g) was dissolved in THF (1.6 L) and treated with n-Butyllithium (n-BuLi, 246 mL of 2.5 M solution in hexane, 2.5 e.q.) at -78°C and stirred for one hour. The resulting mixture was quenched with iodomethane (46 mL) for 0.5 hour. The solution was extracted with ethyl acetate and Na2S2C"3 and NaHCC"3. The mixture was evaporated under reduced vacuum to give the product l,5-dihexyl-2,6-bis(methoxymethoxy)naphthalene (90%>). LRMS (ESI): Calcd. for Ci6H20O4: 276.1362, Found: 276.1.
Example 4 - 3,7-dibromo-2,6-bis(methoxymethoxy)-l,5-dimethylnaphthalene
Figure imgf000058_0002
[00126] N-BuLi (140 mL of 2.5 M solution) was added at room temperature to a solution of 2,6-bis(methoxymethoxy)-l,5-dimethylnaphthalene (29 g) in anhydrous ethyl ether (Et20, 1 L). After 3 h, the solution was cooled to 0°C. A THF (100 ml) solution of l,2-dibromo-l, l,2,2-tetrafluoroethane (108 g) was added to the above mixture, and the resulting mixture was allowed to warm to room temperature over 4 h. Saturated sodium thiosulfate was then added to quench the reaction, and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with brine and dried over Na2S04. After evaporation, the resulting crude product was purified by column chromatography on silica gel to give the final product 3,7-dibromo- 2,6-bis(methoxymethoxy)-l,5-dimethylnaphthalene (45%). LRMS (ESI): Calcd. for Ci6Hi8Br204: 433.9551, Found: 434.0.
Example 5 - 3,7-dibromo-l,5-dimethylnaphthalene-2,6-diol
Figure imgf000058_0003
[00127] A mixture of 3,7-dibromo-2,6-bis(methoxymethoxy)-l ,5-dimethyl naphthalene (3 g) and hydrochloric acid (6N HC1, 30 mL) in dichloromethane/methanol (15 ml/75 ml) was heated to 50°C and stirred overnight. The resulting mixture was poured into water and extracted with ethyl acetate. The organic extracts were washed with brine and dried over Na2S04. The solvents were evaporated to give the crude product 3,7- dibromo-l ,5-dimethylnaphthalene-2,6-dio 1.(90%). LRMS (ESI): Calcd. for Ci2HioBr202: 345.9027, Found: 345.9.
Example 6 - 3,7-Dibromo-l,5-dimethylnaphthalene-2,6-diyl bis(trifluoro methanesulfonate)
Figure imgf000059_0001
[00128] To a suspension of 3,7-dibromo-l ,5-dimethylnaphthalene-2,6-diol (3.24 g), pyridine (4.5 mL) in dichloromethane (90 mL) was slowly added trifluoromethanesulfonic anhydride (3.6 mL) at 0°C. After the mixture was stirred for 4 h at room temperature, water and hydrochloric acid (1 M) were added. The resulting mixture was extracted with dichloromethane and combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography on silica gel to give 3,7-Dibromo-l ,5-dimethylnaphthalene-2,6-diyl bis(trifluoromethanesulfonate) (80%). LRMS (ESI): Calcd. for Ci4H8Br2F606S2: 609.8013, Found: 609.9.
Example 7 - ((3,7-dibromo-l,5-dimethylnaphthalene-2,6-diyl)
bis(ethyne-2,l-diyl))bis(triisopropylsilane)
Figure imgf000059_0002
[00129] To a degassed solution of 3,7-Dibromo-l ,5-dimethylnaphthalene-2,6-diyl bis(trifluoro methanesulfonate) (28 mg) in dimethylformamide (DMF, 1 mL) and diisopropylamine (0.7 mL) was added bis(triphenylphosphine) palladium chloride (Pd(PPh3)2Cl2, 25 mg), copper(I) iodide (Cul) (9 mg) and ethynyltriisopropylsilane (70 μί). After the mixture was stirred for 50 min at room temperature, water and hydrochloric acid (1 M) were added. The resulting mixture was extracted with ethyl acetate and the combined organic layer was dried (MgSC^) and concentrated in vacuo. The residue was purified by column chromatography on silica gel to give ((3,7- dibromo-l,5-dimethylnaphthalene-2,6-diyl)bis(ethyne-
2,l-diyl))bis(triisopropylsilane) (50%). LRMS (ESI): Calcd. for C34H5oBr2Si2: 631.1250 (MW-pr), Found: 631.1 (MW-43).
Example 8 - 4,8-dimethyl-N2,N6-dipentyl-3,7-bis((triisopropylsilyl) ethynyl) naphthalene-2,6-diamine
Figure imgf000060_0001
[00130] A solution of ((3,7-dibromo-l,5-dimethylnaphthalene-2,6-diyl)bis(ethyne-2,l- diyl))bis(triisopropylsilane) (0.73 mmol), t-NaOBu (304 mg), Pd2dba3 (54 mg) and (S)- BINAP (78 mg) in dry toluene (8 mL) was purged with nitrogen for 10 min. Pentan-1- amine (0.58 ml) was added via a syringe and the mixture was re fluxed under nitrogen for 4 hours. After cooling to room temperature, water was added to the solution and the reaction mixture was extracted twice with diethyl ether. After the organic phases were dried over MgSC^, the solvents were removed using a rotary evaporator. . The residue was purified by column chromatography on silica gel to give 4,8-dimethyl-N2,N6- dipentyl-3,7-bis((triisopropylsilyl)ethynyl)naphthalene-2,6-diamine (40%). LRMS (ESI): Calcd. For C44H74N2S12: 686.5391, Found: 686.6.
Example - 3,7-di(hex-l-yn-l-yl)-l,5-dimethylnaphthalene-2,6-diol
Figure imgf000060_0002
[00131] Compounds 3,7-dibromo-l,5-dimethylnaphthalene-2,6-diol (560 mg),
[Pd(PPh3)4] (31.0 mg), Cul (24 mg), PPh3 (31mg), iPr2NH (5.8 mL), and Et3N (16.1 mL) were added to a three necked flask, equipped with a condenser and a magnetic stirrer under an inert atmosphere. The mixture was purged with Ar and stirred for 30 min, while compound hex-l-yne (1.1 mL) was added in one portion. After the addition, the reaction mixture was slowly heated to 80°C and stirred for 15 min at this temperature. After cooling to room temperature, the solvent was removed under reduced pressure to afford the residue, which was extracted with DCM, and washed twice with water. The organic layer was dried (MgSC^). After removal of solvent, the product was purified by flash column chromatography to give 3,7-di(hex-l-yn-l-yl)- l,5-dimethylnaphthalene-2,6-diol (90%). LRMS (ESI): Calcd. For C24H2802: 348.2089, Found: 348.2.
Example 10 - 3,7-di(hex-l-yn-l-yl)-l,5-dimethylnaphthalene-2,6-diyl
bis(trifluoromethanesulfonate)
Figure imgf000061_0001
[00132] To a suspension of 3,7-di(hex-l-yn-l-yl)-l,5-dimethylnaphthalene-2,6-diol (210 mg), pyridine (0.3 mL) in dichloromethane (6 mL) was slowly added trifluoromethanesulfonic anhydride (0.21 mL) at 0°C. After the mixture was stirred for 2 h at room temperature, water and hydrochloric acid (1 M) were added. The resulting mixture was extracted with dichloromethane and combined organic layer was dried (MgSC^) and concentrated in vacuo. The residue was purified by column chromatography to give 3,7-di(hex-l-yn-l-yl)-l,5-dimethylnaphthalene-2,6-diyl bis(trifluoromethanesulfonate) (40%) LRMS (ESI): Calcd. For C26H26F606S2: 612.1075, Found: 612.0.
Example 11 - 3,7-di(hex-l-yn-l-yl)-l,5-dimethyl-N2,N6-dipentylnaphthalene-2,6- -amine
Figure imgf000061_0002
[00133] A solution of 3,7-di(hex-l-yn-l-yl)-l,5-dimethylnaphthalene-2,6- diylbis(trifluorometh-anesulfonate) (367 mg), Cs2C03 (960 mg), Pd2dba3 (133 mg) and (S)-BINAP (385 mg) in dry toluene (7 ml) was purged with nitrogen for 20 min. Pentan-1 -amine (0. 48 mL) was added via a syringe and the mixture was refluxed under nitrogen for 7 h. After cooling to room temperature, water was added to the solution and the reaction mixture was extracted twice with diethyl ether. After the organic phases were dried over MgS04, the solvents were removed using a rotary evaporator. The crude product was purified by column chromatography and the desired product of 3 ,7-di(hex- 1 -yn- 1 -yl)- 1 ,5-dimethyl-N2,N6-dipentylnaphthalene-2,6-di-amine was obtained (24%). LRMS (ESI): Calcd. For C34H5oN2: 486.3974, Found: 486.4.
Example 12 - 2,7-dibutyl-5,10-dimethyl-l,6-dipentyl-l,6-dihydroindolo[6,5- f| indole
Figure imgf000062_0001
[00134] In an dried pressure tube, to a solution of 3,7-di(hex-l-yn-l-yl)-l ,5- dimethyl-N2,N6-dipentylnaphthalene-2,6-diamine (10 mg) in DMSO (2 mL) was added finely crushed KOH (100 mg).The resulting reaction mixture was heated at 120°C for 16 h and was extracted with ethyl acetate and the combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography on silica gel to give 4,9-dimethyl-l ,6-dipentyl-l ,6-dihydroindolo[6,5- fjindole. LRMS (ESI): LRMS (ESI): Calcd. For C34H5oN2: 486.3974, Found: 486.4.
Example 13 - l,5-dibromonaphthalene-2,6-diyl bis(trifluoromethanesulfonate)
Figure imgf000062_0002
[00135] To a suspension of l ,5-dibromonaphthalene-2,6-diol (10.1 g), pyridine
(15.3 mL) in dichloro methane (305 mL) was slowly added trifluoromethanesulfonic anhydride (12.2 mL) at 0°C. After the mixture was stirred for 8 h at room temperature, water and hydrochloric acid (1 M) were added. The resulting mixture was extracted with dichloro methane and combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography to give 1 ,5- dibromonaphthalene-2,6-diyl bis(trifluoromethanesulfonate) (50%) LRMS (ESI): Calcd. For Ci2H4Br2F606S2: 581.7700, Found: 581.8.
Example 14 - l,5-dibromo-2,6-di(hex-l-yn-l-yl)naphthalene
Figure imgf000062_0003
[00136] To a degassed solutionof l ,5-dibromonaphthalene-2,6-diyl bis(trifluoromethanesulfonate) (582 mg) in DMF (7 mL) and diisopropylamine (7 mL) was added Pd(PPh3)2Cl2 (70 mg), Cul (38 mg) and hex-l-yne (222 μΐ,). Reaction was stirred at room temperature and monitored by GCMS. Water and hydrochloric acid (1 M) were added. The resulting mixture was extracted with dichloromethane and the combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography on silica gel eluted with hexane to give 1 ,5- dibromo-2,6-di(hex-l-yn-l-yl)naphthalene (50%) LRMS (ESI): Calcd. For C22H22Br2: 446.2181 , Found: 446.1.
Example 15 - 2,6-di(hex-l-yn-l-yl)-Nl,N5-dipentylnaphthalene-l,5-diamine
Figure imgf000063_0001
[00137] A solution of l ,5-dibromo-2,6-di(hex-l-yn-l-yl)naphthalene (710 mg), t-BuONa (367 mg), Pd2dba3 (73 mg) and (S)-BINAP (198 mg) in dry toluene (6 ml) was purged with nitrogen for 20 min. Pentan-1 -amine (0.58 mL) was added via a syringe and the mixture was refluxed under nitrogen for 7 h. After cooling to room temperature, water was added to the solution and the reaction mixture was extracted twice with diethyl ether. After the organic phases were dried over MgS04, the solvents were removed using a rotary evaporator. The crude product was purified by column chromatography and the desired product of 2,6-di(hex-l-yn-l-yl)-Ni,N5- dipentylnaphthalene-l ,5-diamine was obtained (50%). LRMS (ESI): Calcd. For C32H46N2: 458.3661 , Found: 458.4.
Example 16 - 2,7-dibutyl-3,8-dipentyl-3,8-dihydroindolo[7,6-g] indole
Figure imgf000063_0002
[00138] In an dried pressure tube, to a solution of 2,6-di(hex-l-yn-l-yl)-Ni,N5- dipentylnaphthalene-l ,5-diamine (580 mg) in DMSO (3 mL) was added finely crushed KOH (364 mg).The resulting reaction mixture was heated at 120°C for 20 h and was extracted with ethyl acetate and the combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography on silica gel to give 2,7-dibutyl-3,8-dipentyl-3,8-dihydroindolo[7,6-g]indole (70 %). LRMS (ESI): Calcd. For C32H46N2: 458.3661 , Found: 458.4.
Example 17 - 2,6-dibromonaphthalene-l,5-diol
Figure imgf000064_0001
[00139] To a suspension of naphthalene-l ,5-diol (1 15.2 g) in CH3CN (800 mL) was added DMF solution (400 mL) of NBS (254 g) dropwise and the mixture was stirred at room temperature and monitored by GCMS. Water was added quench the reaction. The resulting precipitate was collected by filtration and washed with water to give 2,6-dibromonaphthalene-l ,5-diol (80%) LRMS (ESI): Calcd. For Ci0H6Br2O2: 317.9614, Found: 317.9.
Example 1 - 2,6-dibromonaphthalene-l,5-diyl bis(trifluoromethanesulfonate)
Figure imgf000064_0002
[00140] To a suspension of 2,6-dibromonaphthalene-l ,5-diol (4.3 g), pyridine
(6.5 mL) in dichloromethane (130 mL) was slowly added trifluoromethanesulfonic anhydride (4.7 mL) at 0°C. After the mixture was stirred at room and monitored by GCMS. Water and hydrochloric acid (1 M) were added. The resulting mixture was extracted with dichloromethane and combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography to give 2,6-dibromo-naphthalene-l ,5-diyl bis(trifluoromethanesulfonate) (80%) LRMS (ESI): Calcd. For Ci2H4Br2F606S2: 582.0850, Found: 581.9.
Example 19 - 2,6-dibromo-l,5-di(hex-l-yn-l-yl)naphthalene
Figure imgf000064_0003
[00141] assed solutionof 2,6-dibromo-naphthalene-l,5-diyl bis(trifluoromethane-sulfonate) (3 g) in DMF (36 mL) and diisopropylamine (36 mL) was added Pd(PPh3)2Cl2 (360 mg), Cul (196 mg) and hex-l-yne (1.25 mL). The reaction was stirred at room temperature and monitored by GCMS. Water and hydrochloric acid (1 M) were added. The resulting mixture was extracted with dichloromethane and the combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography on silica gel eluted with hexane to give 2,6-dibromo-l,5-di(hex-l-yn-l-yl)naphthalene (71 %) LRMS (ESI): Calcd. For C22H22Br2: 446.2181, Found: 446.1.
Exam - l,5-di(hex-l-yn-l-yl)-N2,N6-dipentylnaphthalene-2,6-diamine
Figure imgf000065_0001
[00142] A solution of 2,6-dibromo-l,5-di(hex-l-yn-l-yl)naphthalene (1.42 g), t-
BuONa (1.42 g), Pd2dba3 (146 mg) and (S)-BINAP (400 mg) in dry toluene (12 mL) was purged with nitrogen for 5 min. Pentan-1 -amine (1.16 mL) was added via a syringe and the mixture was refluxed under nitrogen for 14 h. After cooling to room temperature, water was added to the solution and the reaction mixture was extracted twice with diethyl ether. After the organic phases were dried over MgS04, the solvents were removed using a rotary evaporator. The crude product was purified by column chromatography and the desired product of l,5-di(hex-l-yn-l-yl)-N2,N6- dipentylnaphthalene-2,6-diamine was obtained (70%). LRMS (ESI): Calcd. For C32H46N2: 458.3661, Found: 458.4.
Examp - 2,7-dibutyl-l,6-dipentyl-l,6-dihydroindolo[5,4-e]indole
Figure imgf000065_0002
[00143] In an dried pressure tube, to a solution of l,5-di(hex-l-yn-l-yl)-N2,N6- dipentylnaphthalene-2,6-diamine (100 mg) in DMSO (3 mL) was added finely crushed KOH (100 mg). The resulting reaction mixture was heated at 120°C for 17 h and was extracted with ethyl acetate and the combined organic layer was dried (MgS04) and concentrated in vacuo. The residue was purified by column chromatography on silica gel to give 2,7-dibutyl-l,6-dipentyl-l,6-dihydroindolo[5,4-e]indole (50%). LRMS (ESI): Calcd. For C32H46N2: 458.3661, Found: 458.3.

Claims

What is claimed is:
1. A compound of formula:
Figure imgf000067_0001
Figure imgf000067_0002
Figure imgf000067_0003
Figure imgf000067_0004
Figure imgf000067_0005
wherein each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; y is H, halo, trialkylsilane, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs; and
each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
2. The compound of claim 1, wherein the compound is la or lb.
3. The compound of claim 1, wherein the compound is 2a, 2b, or 2c.
4. The compound of claim 1 , wherein:
Xi is S, Se, NRi, PRi, AsRi, SbRi, O, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri;
X2 is N or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri;
y is H, halo, trialkylsiane, optionally substituted C1-C40 alkyl, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, halo, OSO-alkyl, Mg- halo, Zn-halo, Sn(alkyl)3, B(OH)2, or B(alkoxy)2; and
each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
5. The compound of claim 4, wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, optionally substituted heterocyclyl, or an optionally substituted aryl or optionally substituted heteroaryl from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or naphthyridinyl.
6. The compound of claim 1, wherein the hole reorganization energy is less than 0.35 eV.
7. The compound of claim 6, wherein the hole reorganization energy is from about 0.05 eV to about 0.35 eV.
A polymer of formula:
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000070_0002
Figure imgf000070_0003
Figure imgf000070_0004
wherein n is an integer greater than zero; k is from 1 to 10; m is from 0 to 10; with the proviso that when m is 0, k is null;
each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri;
each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; and
comonomer comprises an optionally substituted C2-C40 conjugated alkenyl, optionally substituted C2-C40 conjugated cycloalkenyl, optionally substitute C2-C40 conjugated heteroalkenyl, optionally substituted conjugated C2-C40 heterocycloalkenyl, optionally substituted C6-C40 aryl, optionally substituted C6-C40 heteroaryl, or:
Figure imgf000072_0001
Figure imgf000072_0002
wherein each m is independently is 1, 2, or 3; o is 0, 1, 2, or 3; Rci , Rc2, Rc3, and are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
9. The polymer of claim 8, wherein:
Rci , Rc2, Rc3, and R^ are independently H, optionally substituted C1-C40 alkyl, C2-C40 optionally substituted alkenyl, optionally substituted C2-C40 alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocyclyl, or optionally substituted phenyl, optionally substituted thiophenyl, optionally substituted furanyl, optionally substituted pyrrolyl, optionally substituted imidazolyl, optionally substituted triazolyl, optionally substituted oxaxolyl, optionally substituted thiazolyl, optionally substituted naphthalenyl, optionally substituted isoquinolinyl, optionally substituted quinolinyl, or optionally substituted naphthyridinyl.
10. The polymer of claim 8, wherein:
Xi is NRi, PRi, AsRi, SbRi, O, S, Se, or Te, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri;
X2 is N or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; and
each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
11. The polymer of claim 10, wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, optionally substituted heterocyclyl, or an optionally substituted aryl or optionally substituted heteroaryl from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl, triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or naphthyridinyl.
12. The polymer of claim 8, wherein n is from 1 to 500; k is from 1-10; and m is from 0- 10; with the proviso that if m is 0, then k is null.
13. The polymer of claim 8, wherein ratio of compound la, lb, 2a, 2b, or 2c to comonomer is from about 10: 1 to 1 : 10.
14. A method of making a compound of structure:
Figure imgf000074_0001
comprising allowing a compound of structure:
Figure imgf000074_0002
to undergo a substitution reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, hetero aryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; each Z is independently Z\ or I, each Z\ is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
15. A method of making a compound of structure:
Figure imgf000075_0001
comprising allowing a compound of structure:
Figure imgf000075_0002
or structure:
Figure imgf000075_0003
to undergo a ring cyclization reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; each Z is independently Z\ or I, each Z\ is independently CI or Br; and each y is independently H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
16. A method of making a compound of structure:
Figure imgf000076_0001
comprising allowing a compound of structure:
Figure imgf000076_0002
to undergo a substitution reaction,
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero arylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each Z is independently Z\ or I, each Z\ is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
17. A method of making a compound of structure:
Figure imgf000077_0001
with a compound of structure:
Figure imgf000077_0002
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; and each y is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri ; each u is independently H, halo, OSO-alkyl, Mg-halo, Zn- halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf;
wherein comonomer comprises an optionally substituted C2-C4o conjugated alkenyl, optionally substituted C2-C4o conjugated cycloalkenyl, optionally substitute C2-C4o conjugated hetero alkenyl, optionally substituted conjugated C2-C4o heterocycloalkenyl, optionally substituted C6-C4o aryl, optionally substituted C6-C4o heteroaryl, or:
Figure imgf000079_0001
Figure imgf000079_0002
wherein each m is independently 1, 2, or 3; o is 0, 1, 2, or 3; Rci, Rc2, Rc3, and are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
18. A method of making a compound of structure:
Figure imgf000080_0001
comprising allowing a compound of structure:
Figure imgf000080_0002
to undergo a substitution reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; and each Z is independently Zi or I, each Zi is independently CI or Br.
19. A method of making a compound of structure:
Figure imgf000080_0003
comprising allowing a compound of structure:
Figure imgf000081_0001
or structure:
Figure imgf000081_0002
to undergo a ring cyclization reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; and each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
20. A method of making a compound of structure:
Figure imgf000082_0001
comprising allowing a compound of structure:
Figure imgf000082_0002
to undergo a substitution reaction,
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
21. A method of making a compound of structure:
Figure imgf000083_0001
comprising polymerizing a compound of structure:
Figure imgf000083_0002
with a compound of structure:
Figure imgf000083_0003
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each y is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2,
B(alkoxy)2, OTs, or OTf; each u is independently H, halo, OSO-alkyl, Mg-halo, Zn- halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf;
wherein comonomer comprises an optionally substituted C2-C4o conjugated alkenyl, optionally substituted C2-C4o conjugated cycloalkenyl, optionally substitute C2-C4o conjugated hetero alkenyl, optionally substituted conjugated C2-C4o heterocycloalkenyl, optionally substituted C6-C40 aryl, optionally substituted C6-C40 heteroaryl, or:
Figure imgf000084_0001
Figure imgf000084_0002
wherein each m is independently 1, 2, or 3; o is 0, 1, 2, or 3; Rci, Rc2, Rc3, and are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
22. A method of making a compound of structure:
Figure imgf000085_0001
to undergo a substitution reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; and each Z is independently Zi or I, each Zi is independently CI or Brand each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
23. A method of making a compound of structure:
Figure imgf000086_0001
to undergo a ring cyclization reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi , PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
24. A method of making a compound of structure:
Figure imgf000087_0001
comprising allowing a compound of structure:
Figure imgf000087_0002
to undergo a substitution reaction,
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, hetero aryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero ary It hiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
25. A method of making a compound of structure:
Figure imgf000088_0001
with a compound of structure:
Figure imgf000088_0002
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each y is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2,
B(alkoxy)2, OTs, or OTf; each u is independently H, halo, OSO-alkyl, Mg-halo, Zn- halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf;
wherein comonomer comprises an optionally substituted C2-C4o conjugated alkenyl, optionally substituted C2-C4o conjugated cycloalkenyl, optionally substitute C2-C4o conjugated hetero alkenyl, optionally substituted conjugated C2-C4o heterocycloalkenyl, optionally substituted C6-C4o aryl, optionally substituted C6-C4o heteroaryl, or:
Figure imgf000090_0001
Figure imgf000090_0002
wherein each m is independently 1, 2, or 3; o is 0, 1, 2, or 3; Rci, Rc2, Rc3, and are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
26. A method of making a compound of structure:
Figure imgf000091_0001
comprising allowing a compound of structure:
Figure imgf000091_0002
to undergo a substitution reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; and each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
27. A method of making a compound of structure:
Figure imgf000092_0001
comprising allowing a compound of structure:
Figure imgf000092_0002
or structure:
Figure imgf000092_0003
to undergo a ring cyclization reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; and each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
28. A method of making a compound of structure:
Figure imgf000093_0001
comprising allowing a compound of structure:
Figure imgf000093_0002
to undergo a substitution reaction,
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each Z is independently Z\ or I, each Z\ is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
29. A method of making a compound of structure:
Figure imgf000094_0001
comprising polymerizing a compound of structure:
Figure imgf000094_0002
with a compound of structure:
Figure imgf000094_0003
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each y is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2,
B(alkoxy)2, OTs, or OTf; each u is independently H, halo, OSO-alkyl, Mg-halo, Zn- halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf;
wherein comonomer comprises an optionally substituted C2-C4o conjugated alkenyl, optionally substituted C2-C4o conjugated cycloalkenyl, optionally substitute C2-C4o conjugated hetero alkenyl, optionally substituted conjugated C2-C4o heterocycloalkenyl, optionally substituted C6-C4o aryl, optionally substituted C6-C4o heteroaryl, or:
Figure imgf000096_0001
Figure imgf000096_0002
wherein each m is independently 1, 2, or 3; o is 0, 1, 2, or 3; Rci , Rc2, Rc3, and are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
30. A method of making a compound of structure:
Figure imgf000097_0001
comprising allowing a compound of structure:
Figure imgf000097_0002
to undergo a substitution reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri ; and each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
31. A method of making a compound of structure:
Figure imgf000098_0001
comprising allowing a compound of structure:
or structure:
Figure imgf000098_0002
to undergo a ring cyclization reaction;
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C4o alkenyl, optionally substituted C2-C4o alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi , PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; and each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, amino carbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
32. A method of making a compound of structure:
Figure imgf000099_0001
comprising allowing a compound of structure:
Figure imgf000099_0002
to undergo a substitution reaction,
wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each R2 is independently optionally substituted C1-C40 alkyl or optionally substituted aryl; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each Z is independently Zi or I, each Zi is independently CI or Br; and each y is independently is H, halo, trialkylsilane optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, hetero aryloxy, optionally substituted heterocyclyl, thiol, alkylthio, hetero ary It hiol, optionally substituted sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, or OTs.
33. A method of making a compound of structure:
Figure imgf000100_0001
comprising polymerizing a compound of structure:
Figure imgf000100_0002
with a compound of structure: wherein each Ri is independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted hetero aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone; each Xi is independently NRi, PRi, AsRi, Sb, O, S, Te, or Se, with the proviso that due to conjugation, Xi may be bonded to one or more additional Ri; each X2 is independently N, P, As, SiRi, or CRi, with the proviso that due to conjugation, X2 may be bonded to one or more additional Ri; each y is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl)3, B(OH)2,
B(alkoxy)2, OTs, or OTf; each u is independently H, halo, OSO-alkyl, Mg-halo, Zn- halo, Sn(alkyl)3, B(OH)2, B(alkoxy)2, OTs, or OTf;
wherein comonomer comprises an optionally substituted C2-C4o conjugated alkenyl, optionally substituted C2-C4o conjugated cycloalkenyl, optionally substitute C2-C4o conjugated hetero alkenyl, optionally substituted conjugated C2-C4o heterocycloalkenyl, optionally substituted C6-C40 aryl, optionally substituted C6-C40 heteroaryl, or:
Figure imgf000102_0001
Figure imgf000102_0002
wherein each m is independently 1, 2, or 3; o is 0, 1, 2, or 3; Rci , Rc2, Rc3, and are independently H, halo, optionally substituted C1-C40 alkyl, optionally substituted aralkyl, alkoxy, alkylthio, optionally substituted C2-C40 alkenyl, optionally substituted C2-C40 alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted aryl, aryloxy, optionally substituted amino, carboxyalkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halo, acyl, optionally substituted heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol, alkylthio, heteroarylthiol, optionally substituted sulfoxide, or optionally substituted sulfone.
34. A device comprising a compound of any of claim 1.
35. A device comprising a polymer of claim 8.
PCT/US2013/034347 2012-03-29 2013-03-28 Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof WO2013149001A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP13717903.2A EP2831078A2 (en) 2012-03-29 2013-03-28 Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof
JP2015503575A JP2015519300A (en) 2012-03-29 2013-03-28 Novel fused naphthalenecycloheterocyclic compounds and methods and uses thereof
US14/387,102 US20150045560A1 (en) 2012-03-29 2013-03-28 Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof
CN201380018052.5A CN104797583A (en) 2012-03-29 2013-03-28 Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261617202P 2012-03-29 2012-03-29
US61/617,202 2012-03-29

Publications (2)

Publication Number Publication Date
WO2013149001A2 true WO2013149001A2 (en) 2013-10-03
WO2013149001A3 WO2013149001A3 (en) 2013-11-21

Family

ID=48143363

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/034347 WO2013149001A2 (en) 2012-03-29 2013-03-28 Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof

Country Status (6)

Country Link
US (2) US20150045560A1 (en)
EP (1) EP2831078A2 (en)
JP (1) JP2015519300A (en)
CN (1) CN104797583A (en)
TW (1) TW201345910A (en)
WO (1) WO2013149001A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016210753A (en) * 2015-05-13 2016-12-15 国立大学法人横浜国立大学 Indolyl benzothiadiazole derivative, method for producing indolyl benzothiadiazole derivative and organic fluorescent material
US10918280B2 (en) 2015-04-15 2021-02-16 The Johns Hopkins University Non-invasive bio-fluid detector and portable sensor-transmitter-receiver system

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8901544B2 (en) 2011-12-06 2014-12-02 Corning Incorporated Organic thin film transistor with ion exchanged glass substrate
KR20160127106A (en) 2014-02-28 2016-11-02 코닝 인코포레이티드 Diketopyrrolopyrrole semiconducting materials, processes for their preparation and uses thereof
TWI568736B (en) * 2014-04-02 2017-02-01 國立交通大學 Heterocyclic compound and synthesis method thereof
TWI642673B (en) * 2014-04-02 2018-12-01 國立交通大學 Heterocyclic compounds and synthesis method thereof
US9761817B2 (en) 2015-03-13 2017-09-12 Corning Incorporated Photo-patternable gate dielectrics for OFET
WO2017006703A1 (en) * 2015-07-07 2017-01-12 富士フイルム株式会社 Organic semiconductor element, compound, organic semiconductor composition, and organic semiconductor film and method for producing same
WO2017210072A1 (en) * 2016-06-03 2017-12-07 E. I. Du Pont De Nemours And Company Electroactive compounds
KR102529488B1 (en) * 2017-06-07 2023-05-09 스미또모 가가꾸 가부시키가이샤 Method for producing high molecular compounds
KR102631401B1 (en) 2018-08-28 2024-01-29 삼성전자주식회사 Compound and thin film transistor and electronic device
JPWO2023073756A1 (en) * 2021-10-25 2023-05-04

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011147690A1 (en) 2010-05-28 2011-12-01 Syngenta Participations Ag Pyrazolecarboxamide derivatives and their use as microbiocides

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2042623C3 (en) * 1969-09-17 1973-09-27 Kuraray Co., Ltd., Kurashiki, Okayama (Japan) Process for the preparation of aromatic polybenzimidazoles
US3655632A (en) * 1970-09-15 1972-04-11 Kuraray Co Process for the production of aromatic polybenzimidazoles
JP2000186145A (en) * 1998-12-22 2000-07-04 Sumitomo Bakelite Co Ltd Polybenzoxazole precursor and polybenzoxazole resin
JP2006165015A (en) * 2004-12-02 2006-06-22 Konica Minolta Holdings Inc Organic thin film transistor material, organic thin film transistor, field effect transistor, and switching device
JP2006216814A (en) * 2005-02-04 2006-08-17 Konica Minolta Holdings Inc Organic semiconductor material, organic semiconductor thin film, organic thin film transistor, field effect transistor and switching element
JP2007067262A (en) * 2005-09-01 2007-03-15 Konica Minolta Holdings Inc Organic semiconductor material, organic semiconductor film, organic semiconductor device and organic semiconductor thin-film transistor
US8212239B2 (en) * 2007-12-13 2012-07-03 E I Du Pont De Nemours And Company Electroactive materials
US8216753B2 (en) * 2007-12-13 2012-07-10 E I Du Pont De Nemours And Company Electroactive materials
JP5284677B2 (en) * 2008-04-25 2013-09-11 山本化成株式会社 Organic transistor
JP5544650B2 (en) * 2008-11-21 2014-07-09 国立大学法人広島大学 Process for producing new compounds
JP2010180151A (en) * 2009-02-04 2010-08-19 Hokkaido Univ Thiophene ring fused polycyclic aromatic compound
KR101117723B1 (en) * 2009-09-04 2012-03-07 삼성모바일디스플레이주식회사 Organic light emitting device
KR20120129889A (en) * 2009-12-25 2012-11-28 고쿠리츠다이가쿠호진 히로시마다이가쿠 Polymer compound, and thin film and ink composition each containing same
WO2011078246A1 (en) * 2009-12-25 2011-06-30 住友化学株式会社 Polymer compound, and thin film and ink composition each containing same
KR101324782B1 (en) * 2010-01-14 2013-10-31 (주)씨에스엘쏠라 Organic light device and organic light compound for the same
JP2011165747A (en) * 2010-02-05 2011-08-25 Yamamoto Chem Inc Organic transistor
US8754188B2 (en) * 2011-03-24 2014-06-17 Northwestern University Semiconducting compounds and devices incorporating same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011147690A1 (en) 2010-05-28 2011-12-01 Syngenta Participations Ag Pyrazolecarboxamide derivatives and their use as microbiocides

Non-Patent Citations (32)

* Cited by examiner, † Cited by third party
Title
"BEILSTEINS HANDBUCH DER ORGANISCHEN CHEMIE", SPRINGCR-VCRLAG
ARNOLD ET AL., ORG. LETT., vol. 13, 2011, pages 5576
AVOLIO ET AL., J. MED. CHEM., vol. 48, 2005, pages 4547
BEILSTEIN J., ORG. CHEM., vol. 6, 2010, pages 830 - 845
BERROUARD ET AL., ANGEW. CHEM. INT. ED., vol. 50, 2011, pages 1 - 5
BROOKINS ET AL., J. MATER. CHEM., vol. 19, 2009, pages 4197
FARGEAS ET AL., EUR. J. ORG. CHEM., vol. 9, 2003, pages 1711 - 21
GUILARTE ET AL., ORG. LETT., vol. 13, 2011, pages 5100 - 5103
HUANG ET AL., ORG. LETT., vol. 13, 2011, pages 5252
HUO ET AL., ANGEW CHEM. INT. ED., vol. 49, 2010, pages 1500
IKEGASHIRA ET AL., J. MED. CHEM., vol. 49, 2006, pages 6950
J. ORG. CHEM., vol. 72, 2007, pages 442 - 451
JERRY MARCH; MICHAEL B. SMITH: "MARCH'S ADVANCED ORGANIC CHEMISTRY: REACTIONS, MECHANISMS, AND STRUCTURE", WILEY-INTERSCIENCE
KATRITZKY, A. ET AL., J. ORG. CHEM., vol. 53, 1988, pages 794
KOLUNDZIC ET AL., J. AM. CHEM. SOC., vol. 133, 2011, pages 9104 - 11
LEE ET AL., ORG. LETT., vol. 13, 2011, pages 5540
LOUIS F. FIESEI; MARY FIESER: "REAGENTS FOR ORGANIC SYNTHESIS", vol. 1-19, 1967, WILEY
LU ET AL., SYN. METALS, vol. 160, 2010, pages 1438 - 41
LUO ET AL., ORG. LETT, vol. 5, 2003, pages 4709 - 12
M. MALAGOLI; J.L. BREDAS, CHEM. PHYS. LETT., vol. 13, 2000
N.W. GRUHN ET AL., PHYS. REV. LETT., vol. 89, 2002, pages 275503
NAIR ET AL., CHEM. EUR. J., vol. 16, 2010, pages 7992
PENG ET AL., ADV. MATER., vol. 23, 2011, pages 4554
QI ET AL., J. AM. CHEM. SOC., vol. 133, 2011, pages 10050
R.A. MARCUS, REV. MOD. PHYS., vol. 65, 1993, pages 599
RICHARD C. LAROCK: "COMPREHENSIVE ORGANIC TRANSFORMATIONS", 1999, WILEY-VCH
SCHNEIDER ET AL., ORG. LETT., vol. 13, 2011, pages 3588
SHINAMURA, S. ET AL., J. AM. CHEM. SOC., vol. 133, 2011, pages 5024
SHOJI ET AL., J. AMER. CHEM SOC., vol. 133, 2011, pages 5024 - 5035
THOMPSON ET AL., BIOORG. MED. CHEM. LETT., vol. 21, 2011, pages 3764 - 66
VERMA ET AL., ORG. LETT., vol. 13, 2011
ZHAO,Y. ET AL., CHEM. EUR. J., vol. 15, 2009, pages 13356

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10918280B2 (en) 2015-04-15 2021-02-16 The Johns Hopkins University Non-invasive bio-fluid detector and portable sensor-transmitter-receiver system
JP2016210753A (en) * 2015-05-13 2016-12-15 国立大学法人横浜国立大学 Indolyl benzothiadiazole derivative, method for producing indolyl benzothiadiazole derivative and organic fluorescent material

Also Published As

Publication number Publication date
WO2013149001A3 (en) 2013-11-21
JP2015519300A (en) 2015-07-09
US20160369045A1 (en) 2016-12-22
TW201345910A (en) 2013-11-16
CN104797583A (en) 2015-07-22
US20150045560A1 (en) 2015-02-12
EP2831078A2 (en) 2015-02-04

Similar Documents

Publication Publication Date Title
US20160369045A1 (en) Novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof
TWI794292B (en) Organic semiconducting compounds
CN109791990A (en) Light-emitting component and useful composition for manufacturing the light-emitting component
CN109791987A (en) Organic semiconductor compound
US10144800B2 (en) Dihydropyrrolo[2,3-F] indole-diketopyrrolopyrrole semiconducting materials, and methods and uses thereof
CN108358905B (en) Compound, luminescent material, luminescent device and display device
Liu et al. Novel bipolar host materials based on 1, 3, 5-triazine derivatives for highly efficient phosphorescent OLEDs with extremely low efficiency roll-off
CN108586441A (en) A kind of compound, a kind of organic light-emitting display device
EP2887412A1 (en) Semiconducting material
CN103270076B (en) There is the macromolecular compound of Dynamics Simulation of Carbon Clusters and use its organic device
EP2755255B1 (en) Method and Compound
CN113087711B (en) Organic electroluminescent materials and devices
Zhao et al. Cyclooctatetrathiophene-cored three-dimensional hole transport material enabling over 19% efficiency of perovskite solar cells
US9580448B2 (en) Boron ester fused thiophene monomers
Wu et al. Nitrogen introduction of spirobifluorene to form α-, β-, γ-, and δ-aza-9, 9′-spirobifluorenes: New bipolar system for efficient blue organic light-emitting diodes
CN115490704A (en) Organic electroluminescent materials and devices
WO2020046669A1 (en) Semiconducting co-polymers of methylenedihydropyrazines with fused thiophenes
JP7394629B2 (en) Conjugated polymers, film-forming compositions, organic thin films, and organic semiconductor devices

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13717903

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2015503575

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2013717903

Country of ref document: EP