WO2018014028A1 - Composés et dispositifs contenant de tels composés - Google Patents

Composés et dispositifs contenant de tels composés Download PDF

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WO2018014028A1
WO2018014028A1 PCT/US2017/042424 US2017042424W WO2018014028A1 WO 2018014028 A1 WO2018014028 A1 WO 2018014028A1 US 2017042424 W US2017042424 W US 2017042424W WO 2018014028 A1 WO2018014028 A1 WO 2018014028A1
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substituted
unsubstituted
groups
compound according
alkyl
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Thomas R. Hoye
Feng Xu
Sean Patrick ROSS
Xiao Xiao
Merrick PIERSON SMELA
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Regents Of The University Of Minnesota
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    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
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    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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    • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • H10K85/625—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing at least one aromatic ring having 7 or more carbon atoms, e.g. azulene
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    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
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Definitions

  • X can be selected from SiR 5
  • R 4 is as defined above and R 5 is selected from H, substituted or unsubstituted branched or straight alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl (including multiple ring systems), substituted or unsubstituted heteroaryl, or combinations thereof.
  • R 5 is selected from H, substituted or unsubstituted branched or straight alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl (including multiple ring systems), substituted or unsubstituted heteroaryl, or combinations thereof.
  • A, B, and C are independently selected from H, SiR 5
  • X can be selected from SiR 5
  • R 4 is as defined above and R 5 is selected from H, substituted or unsubstituted branched or straight alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl (including multiple ring systems), substituted or unsubstituted heteroaryl, or combinations thereof;
  • A can be O, S, or NR 1 where R 1 is as defined above;
  • ring-A can be selected from benzo- 1,2-naphtheno-, 2,3-naphtheno-, 1,2-anthraceno-, 2,3-anthraceno-, 9,10-phenanthreno- as well as any substituted derivatives thereof.
  • compounds of formula IV are compounds of formula IV
  • X can be selected from hydrogen (H), substituted or unsubstituted alkyl groups, fluoroalkyl groups, substituted or unsubstituted aryl groups, esters, halides, alkoxy groups, aryloxy groups, or combinations thereof; Z can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryls, or combinations thereof.
  • Specific illustrative examples of compounds of formula I, II, III and/or IV can include compounds 100 to 110 and 2000 to 2004,and 2006 to 2007 below.
  • X can be selected from hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, esters, amides, ketones, sulfates, sulfonyls, phosphates, phosphonates, or combinations thereof; Z can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic aromatic groups; A can be independently selected from , and , where X is as indicated above and d is an integer from 0 to 6; and a, b and c are 0 or 1 with the caveat that only 1 of a and b can be, but need not be 1.
  • Specific illustrative examples of compounds of formula V can include compounds 200 to 205 below.
  • R can be an alkyl, aryl, sulfonyl or carbonyl-containing functional group.
  • X and Y can independently be selected from hydrogen, substituted or unsubstituted alkyl groups, aryl groups, esters, halides, alkoxy groups, aryloxy groups, or combinations thereof;
  • D is selected from N-alkyl, N-sulfonyl, N-acyl, N-protecting group, O, C(CO 2 Z) 2 where Z can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic aromatic groups;
  • a, b, c, d, e, f, g and h are independently H or C(O 2 )alkyl, or a and b, g and h, or both a and b and g and h together are embedded in a common, five- or six-membered ring, imide ring (e.g.,—CO–NR– CO—, where R can be H or an al
  • X can be selected from hydrogen, substituted or unsubstituted alkyl groups, aryl groups, esters, esters, halides, alkoxy groups, aryloxy groups, or combinations thereof;
  • Z and Z' can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkoxy groups, substituted or
  • Z and Z’ can be independently selected from substituted or
  • A can be independently selected from substituted or unsubstituted aryl groups, , where Z is as indicated above and d is an integer from 0 to 6, or two adjacent A can together form a conjugated ring structure having at least 3 additional members in the ring; and T is –C(CO 2 Z), a substituted or unsubstituted N, or a substituted or unsubstituted C.
  • Q can be CH 2 ; or T can be CH 2 and Q can be NR 2 , with R 2 being SO 3
  • Each X can independently be selected from SiR 5
  • R 4 and R 5 can independently be selected from H, substituted or unsubstituted branched or straight alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl (including multiple ring systems), substituted or unsubstituted heteroaryl, or combinations thereof.
  • Ar1, Ar2, Ar3, Ar4 are independently selected from aryl substituents (phenyl, naphthyl, anthracenyl, and phenanthrenyl), including substitued aryls.
  • organic devices including one or more disclosed compounds.
  • the organic devices can include organic electronic devices, organic photonic devices, or
  • FIG. 1A shows the architecture of a generic OLED and its functioning is depicted in FIG. 1B, while FIG.1C depicts an organic photovoltaic (OPV) device.
  • OLEDs organic light-emitting diodes
  • OLEDs organic photovoltaic
  • OFETs organic field-effect transistors
  • FIG. 2A shows the thermal cycloisomerization reaction of triyne substrates like 1 to produce isomeric benzyne derivatives; and the first stage is termed a "hexadehydro-Diels–Alder” (HDDA) reaction, as depicted in FIG.2B.
  • HDDA hexadehydro-Diels–Alder
  • FIG.3A shows the preparation of the tetrayne 6 in two steps; results of measuring the absorption and emission spectra of compound 8 (also referred to as compound 100) both in solution (red and green, respectively) and as a film (yellow and blue, respectively) are seen in FIG.3B; a photograph of the actual devices prepared (four, in the quadrants of this single ITO/glass substrate) for this preliminary set of measurements is shown in FIG.3C (top left), the behavior of each was similar when subjected to a voltage bias and current flow (top right of FIG. 3C), the chromaticity diagram is also shown (bottom of FIG.3C); FIG.3D shows results of initial DFT calculations; FIG.3E shows specific illustrative compounds or groups of compounds 9a to 9e.
  • FIG. 4A shows an illustrative synthetic scheme for compounds 12a and 12b
  • FIG. 4B shows an illustrative synthetic scheme for compound 14
  • FIG.4C shows an illustrative synthetic scheme for compound 16a and b, and 17a and b and the solid state and solution emission of compound 16a
  • FIG. 4D an illustrative synthetic scheme for compounds 19a, 19b and 20
  • FIG.4E shows specific illustrative compounds or groups of compounds 21.
  • FIG. 5A shows an illustrative synthetic scheme for compound 24; and FIG. 5B shows specific illustrative compounds or groups of compounds 25.
  • FIG.6A illustrates a HDDA + perylene cascade;
  • FIG.6B shows typical characterization data (UV, PL, CV, DFT) of illustrative compounds illustrated in FIG. 6A;
  • FIG. 6C illustrates Larock Pd-promoted benzannulation of arynes;
  • FIG.6D illustrates the benzannulation of HDDA benzynes to dibenzocarbazoles (1010), fluoranthenes (1011), or dinaphthoperylenes (1013).
  • FIG. 7B shows specific illustrative compounds or groups of compounds 29a, 29b, 29c, 30, 31, and 32;
  • FIG. 7C shows an illustrative synthetic scheme for various compounds;
  • FIG. 7D shows an illustrative synthetic scheme for various compounds;
  • FIG.7E shows an illustrative synthetic scheme for various compounds.
  • FIG. 8A shows tetraphenylcyclopentadienone (TPCPD) (1014) trapping efficiently to give strongly fluorescent solids 15;
  • FIG.8B shows conceptually related chemistry proposed for accessing more highly elaborated polycyclics (e.g., 1016).
  • FIG. 9A shows symmetrical and unsymmetrical A-B-C structures (33) that can be used in the derived fused benzynes shown in FIG.9B to 9E;
  • FIG.9B shows an illustrative synthetic scheme for compound or groups of compounds 34 to 36;
  • FIG.9C shows an illustrative synthetic scheme for compound or groups of compounds 39;
  • FIG. 9D shows an illustrative synthetic scheme for compound or groups of compounds 40;
  • FIG. 9E shows an illustrative synthetic scheme for compound or groups of compounds 41, 42 43 and 44;
  • FIG.9F shows an illustrative synthetic scheme for compound or groups of compounds 46, 47 and 48.
  • FIG.10A shows an illustrative synthetic scheme for compound or groups of compounds 50
  • FIG. 10B shows an illustrative synthetic scheme for compound or groups of compounds 52, 53 and 54
  • FIG.10C shows specific illustrative compounds or groups of compounds 55 and 56
  • FIG. 10D shows an illustrative synthetic scheme for compound or groups of compounds 57
  • FIG.10E shows an illustrative synthetic scheme for compound or groups of compounds 58
  • FIG.10F shows specific illustrative compounds or groups of compounds.
  • FIG. 11A shows Pd(0)-Catalyzed benzyne trimerization
  • FIG. 11B shows unexpected, one-pot Cu-catalysis of both the HDDA cycloisomerization and a hydroalkynylation trapping reaction
  • FIG. 11C shows the regioselective hydroalkynylation of a (unsymmetrical) triyne
  • FIG. 11D shows post-HDDA alkyne/arene cyclization
  • FIG. 11E shows double hydroalkynylation and subsequent cyclization
  • FIG.11F shows dimers via alkyne self-cross- metathesis or Glaser homo-coupling.
  • FIG. 12A illustrates trapping with p-diaminobenzene (1042);
  • FIG. 12B illustrates a bidirectional, bis-benzyne precursor (1044) to push-pull bis-indanone (1045) strategy;
  • FIG.12C illustrates oligomer formation via capture of a bis-benzyne precursor by a diamine;
  • FIG. 12D shows the first deep blue emitting HDDA products (arylalkynyldibenzofurans) produced; oligomers containing these chromophores as the repeat units;
  • FIG. 12E illustrates push-pull highly fused bis indanones; and
  • FIG.12F shows indacenes and spirobifluorenes moieties readily derived from indanones.
  • FIG. 13A shows the domino-HDDA reaction: 1056a-c to 1057a-c;
  • FIG. 13B shows an inside-out motif;
  • FIG.13C shows benzo analogs improve solubility and support a benzyne- to-naphthyne-to-anthracyne-to-tetracyne cascade.
  • FIGs. 14A and 14B illustrate a mid-chain Glaser coupling (and convergent) strategy for synthesis of polydiyne substrates 1065;
  • FIG.14C illustrates a statistical Glaser coupling strategy for 2-step synthesis of oligomeric domino-HDDA substrates 1067;
  • FIG. 14D shows iterative exponential growth strategy for synthesis of monodisperse poly-yne substrates 1070 and acenes 1071.
  • FIGs.15A and 15B are a thermal gravimetric analysis scan (FIG.15A) and a differential scanning calorimetry scan (FIG.15B) for compound 1015a.
  • FIGs.16A– 16C are a thermal gravimetric analysis scan (FIG.16A); a differential scanning calorimetry scan (FIG.16B) for compound 1015b; and a x-ray crystallographic structure for 1015b (FIG.16C).
  • FIGs.17A and 17B are a thermal gravimetric analysis scan (FIG.17A) and a differential scanning calorimetry scan (FIG.17B) for compound 1015c.
  • FIGs.18A, 18B and 18C show the photoluminescence efficiency (solution quantum yield) for compounds 1015a (FIG.18A), 1015b (FIG.18B) and 1015c (Fig.18C) in THF/water mixtures.
  • FIGs.19A, 19B and 19C show electroluminescence for all nine devices including compound 1015a (FIG.19A), 1015b (FIG.19B) and 1015c (FIG.19C) taken at 2 mA/cm 2 .
  • FIGs.20A– 22C show current-voltage and brightness-voltage data for compounds
  • “a,”“an,”“the,” and“at least one” are used interchangeably and mean one or more than one.
  • alkyl is an unsubstituted or substituted saturated hydrocarbon chain radical having from 1 to about 12 carbon atoms; from 1 to about 10 carbon atoms; or from 1 to about 6 carbon atoms.
  • alkyl groups include, for example, methyl, ethyl, propyl, iso-propyl, and butyl.
  • a C 2 to C 4 substituted or unsubstituted alkyl radical for example refers to a C 2 to C 4 linear alkyl chain that may be unsubstituted or substituted. If the C 2 to C 4 linear alkyl chain is substituted with an alkyl radical, the carbon number of the alkyl radical increases as a function of the number of carbons in the alkyl substituent.
  • cycloalkyl refers to a saturated hydrocarbon containing one ring having a specified number of carbon atoms.
  • examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • aryl means a monocyclic, bicyclic, or tricyclic monovalent aromatic radical, such as phenyl, biphenyl, naphthyl, or anthracenyl, which can be optionally substituted with up to five substituents which may be selected from C1- C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, aryl, heteroaryl, hydroxy, C1-C3 hydroxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, amino, and C1-C3 mono alkylamino for example.
  • alkoxy alone or in combination, includes an alkyl group connected to the oxy connecting atom.
  • alkoxy also includes alkyl ether groups, where the term 'alkyl' is defined above, and 'ether' means two alkyl groups with an oxygen atom between them.
  • suitable alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s- butoxy, t-butoxy, methoxymethyl , and methoxyethyl .
  • cyano group or“cyano” refers to a–CN group.
  • halogen or“halide” refers to fluoride, chloride, bromide, or iodide.
  • fluoro “chloro”,“bromo”, and“iodo” may also be used when referring to halogenated substituents, for example,“trifluoromethyl.”
  • heteroaryl refers to aromatic moieties containing one or more heteroatoms (e.g., N, O, S, or the like) as part of the ring structure .
  • “Substituted heteroaryl” refers to heteroaryl groups further bearing one or more substituents as set forth above.
  • heteroaryl may represent a stable 5- to 7-membered monocyclic- or stable 9- to 14-membered fused bicyclic heterocyclic ring system that contains an aromatic ring, any ring of which may be saturated, such as pyridinyl, partially saturated, or unsaturated, or piperidinyl, and which consists of carbon atoms and from one to four heteroatoms selected from the group consisting of N, O, and S, and wherein the nitrogen and sulfur heteroatoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized, and including any bicyclic group in which any of the above-defined heterocyclic rings is fused to a benzene ring.
  • heterocyclic ring may be attached at any heteroatom or carbon atom which results in the creation of a stable structure.
  • heteroaryl groups include, but are not limited to, benzimidazole, benzisotbiazole, benzisoxazole, benzofuran, benzothiazole, benzothiophene, benzotriazole, benzoxazole, carboline, cinnoline, furan, furazan, imidazole, indazole, indole, indolmne, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, phthalazme, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, quinazoline, quinoline, quinoxaline, tetrazole, thiadiazole, thi
  • “hydroxyl group” refers to a substituent group of formula—OH.
  • the cyclic moiety can include all aryl moieties heteroaryl moieties, cyclic moieties, heterocyclic moieties, and combinations thereof.
  • the cyclic moieties can also be substituted or unsubstituted.
  • the number of rings, the number of connections to the main formula, or both will be understood by one of skill in the art based on the nature of the particular cyclic moiety. Additionally, more ring structures can be indicated on a formula than can exist in order to show all possible connection points. For example, in Formula II, it is understood that only one of the two rings shown can be present at one time; the two rings are shown to indicate the two possible connection points of the ring to the main structure.
  • Suitable substituents include, without limitation, halo, hydroxy, oxo (e.g., an annular -CH- substituted with oxo is -C(O)-), nitro, halohydrocarbyl, hydrocarbyl, aryl, aralkyl, alkoxy, aryloxy, amino, acylamino, alkylcarbamoyl, arylcarbamoyl, aminoalkyl, acyl, carboxy, hydroxyalkyl, alkanesulfonyl, arenesulfonyl, alkanesulfonamido, arenesulfonamido, aralkylsulfonamido, alkylcarbonyl, acyloxy, cyano, and ureido groups.
  • any method disclosed herein that includes discrete steps the steps may be conducted in any feasible order, unless context indicates otherwise. And, as appropriate, any combination of two or more steps may be conducted simultaneously.
  • novel compounds and groups of compounds can be useful, for example in organic devices.
  • Organic Devices are disclosed herein.
  • Organic devices as described herein can include both organic electronic devices and organic photonic devices.
  • the field of organic electronic and photonic materials dates from the discovery of photoconduction in anthracene reported in 1906. Nonetheless, it is burgeoning today at an amazing pace.
  • PV photovoltaic
  • LEDs light-emitting diodes
  • FETs field-effect transistors
  • Organic electronic and photonic materials already find application in many electronic devices and displays.
  • Organic light-emitting diodes are now found in many smaller hand-held electronic displays; notably, Samsung Galaxy smartphones and tablets, starting with the Note in 2011, use OLED technology.
  • OLED big-screen televisions have recently made their way onto the market (Samsung and LG).
  • robust, deep blue- emitting (shorter ⁇ end of the visible spectrum) organic LEDs remain an arena in need of considerable improvement. Creating emitters of highly saturated blue light has always been challenging.
  • the 2014 Nobel Prize in physics was awarded "for the invention of efficient blue light-emitting diodes, which has enabled bright and energy-saving white light sources.”
  • Manifold lighting applications for OLEDs are on the horizon. Solar energy panels based on organic photovoltaics represent the Holy Grail with the greatest potential.
  • FIG.1A The architecture of a generic OLED is depicted in FIG.1A and its functioning in FIG. 1B.
  • This particular device contains a green (a) electron transporter layer that assists in injecting electrons from the Al cathode into unoccupied orbitals (UMOs), most easily the LUMO, of molecules of the blue (b) active (emissive) layer.
  • UEOs unoccupied orbitals
  • b active (emissive) layer.
  • the yellow (c) hole-transporter component assists in injecting holes from the anodic ITO into the active layer (b).
  • An organic photovoltaic (OPV) device is, in the simplest sense, an inverse OLED (FIG. 1C).
  • a photon enters, an exciton is created, and an electron-hole pair is formed following charge separation. It is desirable to use molecules whose excited states can undergo ready exciton dissociation, a requirement for charge extraction. Absorption properties that overlap well with large portions of the solar spectrum are also desirable (Small molecule organic semiconductors on the move: Promises for future solar energy technology. Mishra , M.; Bäuerle, P. Angew. Chem. Int. Ed.2012, 51, 2020–2067).
  • OFETs Organic field-effect transistors
  • TFTs thin-film transistors
  • FETs Organic field-effect transistors
  • FETs simple terms
  • the organic semiconductor in an OFET allows current to flow between source and drain in its open state, but the current can be throttled by adjustment of the gate voltage.
  • Good OFET semiconductor compounds often have small HOMO/LUMO band gaps (e.g., through extended ⁇ -conjugation) and planar structures
  • Crystalline small molecules or highly ordered conducting polymers are most typically used as the semiconductor layer.
  • the crystal lattice properties of these compounds are often critical to the success in OFET applications. More specifically, "the molecules should be preferentially oriented with the long axes approximately parallel to the FET substrate normal since the most efficient charge transport occurs along the direction of intermolecular ⁇ - ⁇ –stacking”
  • the thermal cycloisomerization reaction of triyne substrates like 1 to produce isomeric benzyne derivatives 2 (FIG.2A) is an extraordinarily general reaction (The hexadehydro-Diels– Alder reaction. Hoye, T. R.; Baire, B.; Niu, D.; Willoughby, P. H.; Woods, B. P. Nature 2012, 490, 208–212). Both known and new in situ trapping reactions of arynes then convert 2 into a multitude of adducts 3 by engaging both tethered (intramolecular) moieties as well as external (bimolecular) trapping agents. This two-stage cascade process is a remarkably powerful overall transformation.
  • hexadehydro-Diels–Alder (HDDA) cyclizations Impact of the linker structure. Woods, B. P.; Baire, B.; Hoye, T. R. Org. Lett.2014, 16, 4578–4581; Mechanism of the reactions of alcohols with o-benzynes. Willoughby, P. H.; Niu, D.; Wang, T.; Haj, M. K.; Cramer, C. J.; Hoye, T. R. J. Am. Chem.
  • DSC Differential scanning calorimetry
  • HDDA hexadehydro-Diels–Alder
  • Soc.138, 7832-7835 )) a) to discover entirely new types of benzyne reactivity and b) to understand more intimately the mechanistic details for certain types of benzyne trapping reactions.
  • a major feature of the HDDA cascade distinguishes it from classical benzyne chemistry. Namely, HDDA-generated benzynes are formed thermally (and, now, photochemically) and, as a consequence, in the absence of the reagents and byproducts that necessarily accompany all classical methods of aryne synthesis (Synthetic methods for the generation and preparative application of benzyne. Kitamura, T. Aust. J.
  • HDDA products have shown excellent thermal, oxidative, and photochemical robustness.
  • the power of the HDDA cascade provides the ability to promptly deliver multiply substituted (including alkynyl), ⁇ -rich aromatic core structures composing unique chemical space in a single step.
  • the HDDA reaction allows access to far more structurally complex benzynes with far greater ease of synthesis than classical aryne chemistries.
  • Such structures are typically either polymeric/oligomeric in nature [for example, poly(paraphenylene), poly(phenylenevinylene) (PPV), poly(9,9'-dioctylfluorene), poly(9- vinylcarbazole)] or discrete small molecules [for example, 4,4′-bis(N-carbazolyl)-1,1′-biphenyl, tris-(8-hydroxyquinoline)aluminum, 2-(4-tert-butylphenyl)-5-(4-biphenylyl)-1,3,4-oxadiazole, or rubrene (5,6,11,12-tetraphenyltetracene)], acting either alone or in admixture with a dopant whose function can be, for example, to harvest both the singlet and triplet exciton spin states and then subsequently phosphoresce [e.g., tris(2-phenylpyridinato-C 2 ,N)iridium(III
  • novel compounds which may have chromophoric properties, the structures of which can be systematically modified and synthesized.
  • Y can be (R 1 )
  • X can be selected from SiR 5
  • R 4 and R 5 are independently selected from H, substituted or unsubstituted branched or straight alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl (including multiple ring systems), substituted or unsubstituted heteroaryl, or combinations thereof.
  • ring-A and ring-B can be independently selected from benzo-, naphtheno-, or anthracenofurano, -thiofurano, or indolo, where the indolo nitrogen can bear R 2 .
  • Some disclosed embodiments of compounds can include those having a structure of formula II:
  • Y can be (R 1 )
  • X can be selected from SiR 5
  • R 4 and R 5 are independently selected from H, substituted or unsubstituted branched or straight alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl (including multiple ring systems), substituted or unsubstituted heteroaryl, or combinations thereof.
  • Z can be O, S, or NR 1 where R 1 is as indicated above.
  • ring-A can be selected from benzo- 1,2-naphtheno-, 2,3-naphtheno-, 1,2-anthraceno-, 2,3-anthraceno-, 9,10-phenanthreno- as well as any substituted derivatives thereof.
  • Some disclosed embodiments of compounds can include those having a structure of formula III:
  • X can be selected from hydrogen (H), substituted or unsubstituted alkyl groups, fluoroalkyl groups, substituted or unsubstituted aryl groups, esters, halides, alkoxy groups, aryloxy groups, or combinations thereof;
  • Z can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryls, or combinations thereof.
  • X and Y can be selected from hydrogen (H), substituted or unsubstituted alkyl groups, fluoroalkyl groups, substituted or unsubstituted aryl groups, esters, halides, alkoxy groups, aryloxy groups, or combinations thereof;
  • Z can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryls, or combinations thereof.
  • substituents for X can include alkoxyl groups, hydroxyl groups, cyano groups, haloalkyl groups, alkyl groups, halides, protecting groups, or any combinations thereof.
  • Z can independently be selected from substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkyls, or combinations thereof. In some illustrative embodiments Z can independently be selected from substituted or unsubstituted C 1 to C 6 alkyl groups, or substituted aryl groups. In some illustrative embodiments Z can independently be selected from substituted or unsubstituted benzyl groups. In some illustrative embodiments, W can be oxygen (O). In some embodiments, the dashed ring can be a fused aromatic ring such as benzo or naphtho for example.
  • the dashed ring can be a heteroaromatic ring such as pyrido, quinolone, isoquinoline, furano, or thiopheno, for example.
  • the fused aromatic or heteroaroatmic ring can be substituted with, for example 1-3, alkoxy, aryloxy, halo, alkyl, amino, fluoroaklyl, trialkysily, or combinations thereof.
  • Specific illustrative examples of compounds of formula I, II, or III can include compounds 100 to 110, 2000 to 2004, and 2006 to 2007 below.
  • X can be selected from hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, esters, amides, ketones, sulfates, sulfonyls, phosphates, phosphonates, or combinations thereof;
  • Z can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic
  • A can be independently selected from , and , where X is as indicated above and d is an integer from 0 to 6; and a, b and c are 0 or 1 with the caveat that only 1 of a and b can be, but need not be 1.
  • X can independently be selected from hydrogen, substituted or unsubstituted aryl groups such as phenyl, naphthyl, phenanthryl, carbazyl, or combinations thereof.
  • substituents for X can be substituted with alkoxy groups, hydroxyl groups, cyano groups, haloalkyl groups, alkyl groups, halogens, protecting groups, or any combinations thereof.
  • Z can independently be selected from substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkyls, or combinations thereof.
  • Z can independently be selected from substituted or unsubstituted C1 to C 6 alkyl groups, or substituted aryl groups.
  • Z can
  • X independently be selected from substituted or unsubstituted benzyl groups.
  • X at any point of formula II can be substituted.
  • substituents of X can include methoxy, methanoate, N-phenyl, phenyl, naphthyl, carbazyl (e.g., substituted at the nitrogen).
  • Specific illustrative examples of compounds of formula IV can include compounds 200 to 205 below.
  • R can be an alkyl group.
  • Some illustrative embodiments include compounds 200 to 203, for example. Structural similarities of compounds 100, 102, 104, 105, 107, 108, 2001, 2002, 2003, 2004, 2006 and 2007 are shown below.
  • X and Y can independently be selected from hydrogen, substituted or unsubstituted alkyl groups, aryl groups, esters, halides, alkoxy groups, aryloxy groups, or combinations thereof;
  • D is selected from N-alkyl, N-sulfonyl, N-acyl, N-protecting group, O, C(CO 2 Z) 2 , where Z can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic aromatic groups,;
  • a, b, c, d, e, f, g and h are independently H or C(O 2 )alkyl, or a and b, g and h, or both a and b and g and h together are embedded in a common, five- or six-membered ring, imide ring (i.e.,—CO–NR– CO—, where R can be H
  • X and Y can be independently selected from hydrogen, alkoxy, esters, or combinations thereof.
  • only four of a to h are CO 2 alkyl.
  • CO 2 alkyl can be CO 2 CH 2 CH 3 .
  • a and b, g and h, or both a and b and g and h together form a piperidine-2,6-dione group.
  • Specific illustrative examples of compounds of formula III can include compounds 300 to 304 below.
  • Some illustrative embodiments include compounds 300 to 303, for example.
  • X can be selected from hydrogen, substituted or unsubstituted alkyl groups, aryl groups, esters, esters, halides, alkoxy groups, aryloxy groups, or combinations thereof;
  • Z and Z' can independently be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkoxy groups, substituted or
  • Specific illustrative examples of compounds of formula VII can include compounds 400 to 402, for example.
  • Some illustrative embodiments include compounds 400 and 401, for example.
  • A can be independently selected from substituted or unsubstituted aryl groups, , where Z is as indicated above and d is an integer from 0 to 6, or two adjacent A can together form a conjugated ring structure having at least 3 additional members in the ring; and T is –C(CO 2 Z), a substituted or unsubstituted N, or a substituted or unsubstituted C.
  • Specific illustrative examples of compounds of formula VIII can include compounds 500 to 509, for example.
  • Some illustrative embodiments include compounds 500 to 504, for example.
  • Compound 507 above can also be described by the four compounds (507a to 507d) below that explains different fusions that may be encompassed by compound 507 above.
  • the A-B-C component can be described as seen in FIG.9A and R 1 , R 2 , etc. can generally refer to substituted or unsubstituted alkyls.
  • Ar, Ar 1 , Ar 2 , Ar 3 can independently be selected from substituted or unsubstituted aryl groups, including for example heteroaryl groups.
  • Another group of compounds includes compounds 601 to 607.
  • T can be (R 1 )
  • Each X can independently be selected from SiR 5
  • R 4 and R 5 can independently be selected from H, substituted or unsubstituted branched or straight alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl (including multiple ring systems), substituted or unsubstituted heteroaryl, or combinations thereof.
  • Ar1, Ar2, Ar3, Ar4 are independently selected from aryl substituents (phenyl, naphthyl, anthracenyl, and phenanthrenyl), including substitued aryls.
  • A, B, and C are independently selected from H, SiR 5
  • a and B are joined into a benzo-, naphtheno-, or
  • anthracenofurano, -thiofurano, or indolo ring where the indolo nitrogen can bear R 2 and C is selected from those above.
  • B and C are joined into a benzo- or triphenyleno- ring and may contain additional aryl substitutents.
  • the tetrayne 6 was prepared in two steps (bromination of 4 to 5 and Cadiot-Chodkiewicz coupling with 2-methoxyphenylacetylene) and the rate of its HDDA cyclization was studied (FIG.3A). When heated in CDCl 3 , it proceeded to give the
  • alkynyldibenzofuran 8 in an extremely clean transformation (>90% yield of chromatographed material).
  • Adventitious water in the medium was likely responsible for removal of the methyl group from an intermediate oxonium ion derived from the electrophilic benzyne 7 (An unprecedented arylcarbene formation in thermal reaction of non-conjugated aromatic enetetraynes and DNA strand cleavage.
  • alkynyldibenzofuran 8 proved to be very robust, showing virtually no sign of thermal degradation during laboratory sublimation or even following heating in air at 200 °C.
  • An OLED device was built from the compound using standard procedures. The device emitted blue light ( ⁇ max 440 nm) with an external quantum efficiency (EQE, the number of photons out of the glass substrate vs. the number of electrons in) of 0.9%. To put this value into context, blue OLEDs rarely show fluorescence EQEs as high as 5%. Charge-transfer between nearby emissive molecules often lowers photoluminescence (PL) efficiency.
  • PL photoluminescence
  • the theoretical maximum EQE for an ITO-based device capable of capturing essentially all of the fluorescence and phosphorescence potential is only about 20%.
  • the initial fabrication was based on a commonly used architecture comprising 30 nm layer each of TCTA [tris(4- carbazoyl-9-ylphenyl)amine] and TPBi [1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene] as the hole and electron transporter layers, respectively. These encased a 23 nm thick active layer of 8. These layers correspond to the yellow, blue, and green layers depicted in FIG.2A.
  • FIG.3C top left.
  • the four aluminum cathodes are evident as the silver-colored, L-shaped areas on the top surface of the glass.
  • Each of the four devices has a 5 mm x 5 mm area of overlap between its Al and ITO electrodes.
  • Each behaved similarly when subjected to a voltage bias and current flow (onset voltage ca.2.6 V– blue light seen in top right of FIG.3C).
  • the chromaticity diagram (bottom of FIG.3C) gives a more precise characterization of the emission; it is a deep blue (cf. yellow dot), quite near the ideal color saturation point for HDTV application.
  • the oxidation potential of 8 has also be measured (by cyclic voltammetry in acetonitrile) to be 1.27 V (vs. Fc/Fc + ). From the solution absorption spectra the HOMO/LUMO gap it is calculated to be 3.4 eV.
  • the values for the energies of HOMO and LUMO is one of the parameters that can be used to guide the choice and design of additional materials for the electron and hole transporting materials.
  • the degree of planarity in 8 (also referred to as compound 100) will influence its spectroscopic properties.
  • Initial DFT calculations indicated that compound 8 (also referred to as compound 100) prefers a nearly planar relationship between the remote 2-methoxyphenyl and dibenzofuran subunits.
  • the bis-TMS analog will have its arenes essentially orthogonal (FIG. 3D). This could increase the band gap and, perhaps, move the emission color even deeper into the blue/violet region.
  • carbomethoxy groups altogether can be made, this last from 1,6-heptadiyne as the starting material.
  • the electronic substituent effects can also be studied to learn the extent to which they modify the fluorescence properties (1-alkynyl- and 1-alkenyl-3-arylimidazo[1,5- a]pyridines: Synthesis, photophysical properties, and observation of a linear correlation between the fluorescent wavelength and Hammett substituent constants. Yamaguchi, E.; Shibahara, F.; Murai, T. J. Org. Chem.2011, 76, 6146–6158.).
  • HDDA benzynes have also been considered and it has been found that they (cf.11, FIG. 4A) can be captured, in excellent yield, by net addition of a terminal alkyne when a substrate such as the tetrayne 10 and the alkyne are heated in the presence of a catalytic amount of cuprous chloride (Copper-catalyzed three-component coupling of arynes, terminal alkynes and activated alkenes. Bhuvaneswari, S.; Jeganmohan, M.; Cheng, C.-H. Chem. Commun.2008, 5013–5015; Aryne polymerization enabling straightforward synthesis of elusive poly(ortho-arylene)s.
  • the HDDA reaction has also been used in the pursuit of another new class of
  • FIG.5A indicates the feasibility of trapping an HDDA benzyne with perylene (23).
  • Tetrayne 22 was heated and the resulting benzyne trapped to provide 24 as the major product. Although the solubility is marginal in hexanes/EtOAc chromatography eluents, the substance dissolves readily in CDCl 3 .
  • CDCl 3 CDCl 3 .
  • Compound 24 is yellow (and emits orange).
  • the products described in this section may be increasingly visibly colored. This suggests applications in OPV and OFET settings, where smaller HOMO/LUMO gaps are desirable. This often correlates with enhanced carrier mobility. A high degree of crystallinity is also often desirable for use in OFET devices.
  • Adducts like 25 in which two benzyne molecules have been incorporated onto a single perylene scaffold, one to each of its two bay regions, can also be formed. Explicitly shown is the symmetrical 2:1 adduct, but it is noted that by working with isolated 24, it may be possible to prepare mixed adducts in which two different benzyne compounds, each with an attendant unique chromophore, could be incorporated into analogous adducts. Cyclization to yet higher PAH subunits would then follow.
  • the CVs of compounds 1105a vs.1105b show that there is a strong response in this alkynylnaphthoperylene family to the aromatic substituents on both the oxidation and reduction half-wave potentials.
  • the absorption spectra for 1105b and 1105c are very similar, the PL spectra show a marked red-shift for the latter compound. This is consistent with the differences in the HOMO/LUMO maps for (a simplified model of) 1105c, which suggests a substantial amount of charge-transfer character in the excited state; in contrast the maps for the FMOs for the 1105b model (not shown) are very similar.
  • annulation simple o-benzynes e.g, 1108
  • aryl halides red
  • o-halobiphenyl subunit 1107, FIG.6C
  • triphenylenes 1109 Net carbopalladation of 108, followed by cyclization via electrophilic palladation and reductive elimination to the arene atom labeled blue in 1109, finishes the overall [4+2] annulation.
  • the Pd species on this cycle tolerate the high temperature used to produce 1108, which provides a high confidence that HDDA-benzynes will function well in this impressively efficient and versatile process.
  • the arylhalide lacks an ortho arene substituent and the benzyne precursor bears a suitably disposed trapping group, it is proposed that the annulation will proceed by back-biting into that group.
  • the fluoranthene derivative 1012 could a arise from tetrayne 1011 (FIG. 6E).
  • C8 in the naphthyl ring (blue) is envisioned to capture the initial adduct of ArPdI with
  • 1011 Benz Fluoranthene derivatives have been explored as emitters in blue OLEDs.
  • the sense and extent of regioselectivity of the reactions of 1103 Benz or 1011 Benz with ArPdX await to be defined, but we note that potential modifiers include ligands on the Pd and use of a different benzyne from among the >dozen currently in the palette (see FIG.6B).
  • 1012 would be available in only three reactions (alkyne bromination, Cadiot-Chodkiewicz cross- coupling, and HDDA cascade) if this chemistry can be reduced to practice.
  • Three-atom linker structures in the starting tetrayne can be utilized to provide analogs 29a, which still possess the tetraphenylnaphthalene subunit. Contrasting characteristics arising from adducts derived from the cyclone analogs 30 (Pyrene-based fluorescent nitric oxide cheletropic traps (FNOCTs) for the detection of nitric oxide in cell cultures and tissues. Düppe, P. M.; Talbierski, P. M.; Hornig, P.
  • FNOCTs fluorescent nitric oxide cheletropic traps
  • Yamada, M.; Tanaka, Y.; Yoshimoto, Y.; Kuroda, S.; Shimao, I. Bull. Chem. Soc. Jpn.1992, 65, 1006–1011), each of which has planarity locked into the fused ring portion of its "back" rings, can also be considered. This may change the electronic character and nature of the chromophore in analogs 29b. It is noted that phenanthroline ligands (cf. X N) have been used to bind heavy metal atoms such as europium (Lanthanide-based luminescent hybrid materials. Binnemans, K. Chem.
  • FIGs.7C, 7D and 7E illustrate further illustrative compounds.
  • the color of the emission of 1015d is decidedly more green than 1015a–c, which all showed strong blue emission and were further explored as candidates for incorporation into a prototypical OLED. All of these compounds are thermally robust; they can be sublimed with little to no sign of decomposition under a simple mechanical pump vacuum. They gain color only slowly when held in the air at 300 °C. Differential scanning calorimetry (DSC) showed no onset of thermal characteristics below 300 °C and thermal gravimetric analysis (TGA) showed mass loss of 5% only at temperatures ranging from 336– 357 °C. Given these promising characteristics, we worked with a researcher in the lab of Russ Holmes to prepare thin films and measured their photoluminescence efficiencies (K PL ). We then fabricated OLED devices.
  • DSC Differential scanning calorimetry
  • TGA thermal gravimetric analysis
  • each of the arylalkynyl-benzotriphenylene 1016a and -naphthopyrene 1016b (from 2,5-diphenylphenanthro- and 2,5-diphenylpyrenocyclpentadienone, respectively) has an extended planar chromophore that is sterically protected near its midsection by the two orthogonal phenyl substituents. This feature is common to each of the analogous products are anticipated to arise starting from 1017, 1018, or 1019.
  • benzyne adducts of hexaphenylisobenzofuran (1019) can be deoxygenated/reduced (e.g., Zno/AcOH) to the corresponding anthracene adducts and
  • phenanthrolines are ligands for lanthanides and Ir(III). These heavy metals are often used as dopants to the emissive layer, where their promotion of intersystem crossing can turn on phosphorescence by capture of triplet states to dramatically improve K EQE in OLED
  • HDDA hexadehydro-Diels–Alder reaction
  • DSC Differential scanning calorimetry
  • HDDA hexadehydro-Diels–Alder
  • Tetrahedron Lett.2015, 56, 3265–3267 (Memorial Symposium-in-Print for H. H. Wasserman); Mechanism of the intramolecular hexadehydro-Diels–Alder reaction. Marell, D. J.; Furan, L. R.; Woods, B. R.; Lei, X.; Bendelsmith, A. J.; Cramer, C. J.; Hoye, T. R.; Kuwata, K. T. J. Org. Chem.2015, 80, 11744–11754; The pentadehydro-Diels–Alder reaction. Wang, T.; Naredla, R. R.; Thompson, S. K.; Hoye, T. R.
  • the properties of the resulting trapped adducts are influenced at least in part, by the nature of A-B-C.
  • the linkers in the precursors to the benzynes in the top row of FIG.9A are symmetrical and contain propargylic methylene (and sp 3 ) carbons. All of the linkers in the bottom row of FIG.9B have functionality that is conjugated with either the diyne, the
  • the product chromophores can be substantially and easily modified merely by altering the triyne (or tetrayne) substrate and dropping it into virtually any of the reactions already described above or below. It should also be noted that the synthesis of the unsymmetrical substrates may be a bit longer, but virtually every one listed here is available in ⁇ 4-5 total reactions from commercial compounds. Even the tetrayne variants react
  • FIGs.9B to 9F Shown in FIGs.9B to 9F are a variety of possibilities for quickly accessing various structures that may have interesting electro-optical properties.
  • Alkyne cross-metathesis (FIG.9B) could prove to be very powerful—and it should be emphasized that "since the catalysts have evolved from the glovebox to the benchtop, there should be little barrier left for a wider use of this reaction in organic synthesis.” (Alkyne metathesis on the rise. Fürstner, A. Angew. Chem. Int. Ed.2013, 52, 2794–2819).
  • FIG.9C A strategy for conjoining two benzyne intermediates, 37, into products containing a new central benzenoid ring (cf.39) using the 1,4-diarylated mesoionic pyrimidine 38 is shown in FIG.9C.
  • FIG.9D also shows the homotrimerization of HDDA benzynes 37a, a reaction that is well precedented for simple benzynes made by classical methods of elimination (Aryne cycloaddition reactions in the synthesis of large polycyclic aromatic compounds.
  • benzyne itself can be trapped by the 1,8-disubstituted naphthalene derivatives 41 (An interesting benzyne-mediated annulation leading to benzo[a]pyrene. Cobas, A.; Guitián, E.; Castedo, L. J. Org. Chem.1997, 62, 4896–4897) or 43 (Domino Diels–Alder cycloadditions of arynes: New approach to elusive perylene derivatives. Criado, A.; Pe ⁇ a, D.; Cobas, A.; Guitián, E. Chem. Eur.
  • FIG.9F shows a transformation resulting from heating the triynyl ester 46 alone (i.e., in the absence of any trapping agent)
  • Serendipity From an enediyne core biosynthetic hypothesis to the hexadehydro-Diels–Alder reaction. Woods, B. P. Ph.D. Thesis, University of Minnesota, Minneapolis, MN, 2014). This reaction produced the dimeric alkynyl naphthalene derivative 48 in 45% yield following chromatographic purification. This can perhaps be rationalized via cross dimerization of the benzyne 45 with 46 to give a
  • Double-barreled HDDAs Oligomeric Substances
  • FIG.10A Two different types of difunctional reactants have been utilized.
  • One involves the use of 1,4-diaminobenzene. With just 0.5 molar equivalents, the benzyne derived from triyne 49 was efficiently trapped to give the orange-red adduct 50.
  • a complementary strategy FIG. 10B
  • the doubly armed, bis-benzyne precursor 51 was cyclized to deliver the heptacycle 52, again in a reasonably clean fashion.
  • Bis-indanone adducts like 52 can be exploited by converting them into: (a) the quasi-delocalized s-indacene derivatives 53 (s-Indacene, a quasi-delocalized molecule with mixed aromatic and anti-aromatic character.
  • s-Indacene a quasi-delocalized molecule with mixed aromatic and anti-aromatic character.
  • the two types of difunctional substrates described in panels A and B can be joined to produce oligomeric materials like 57. It is thought, but not relied upon that the extended conjugation may lead to strongly absorbing materials across a broad spectral range in solvent-cast films prepared with these oligomers. Analogs synthesized using aliphatic diamines may provide substances with interrupted conjugation for comparative benchmarking of the effect of the linker aryl groups.
  • a series of polymeric materials derived directly from the compound described above (FIG.3) can be synthesized. Namely, compound 99c where X is a bromide or iodide (FIG. 10E) can be oligomerized through Stille or Suzuki coupling (Parker, T. C.; Marder, S. R.
  • FIGs.12A and 12B A relevant preliminary pair of experiments is shown in FIGs.12A and 12B.
  • 1,4-diaminobenzene (1042) was used as the trap.
  • the benzyne 1041 Benz was efficiently captured to give the (orange-red) adduct 1043.
  • the push-pull character of this product, as well as many in this module, is a common structural feature in compounds that have been explored for OLED applications.
  • FIG.12D A type of internal trapping reaction is shown in FIG.12D. It gave the initial, strongly blue fluorescent compounds with which OLED prototypes were prepared. Tetraynes 1047 containing terminal o-methoxyphenyl groups cyclize extremely efficiently to dibenzofurans like 1049. The analogous dibenzothiophenes and carbazoles have also been made from thioether and aniline precursors. Identification of the four methyl-containing byproducts shown beside 1049 provides strong evidence to support the intermediacy of the oxonium ion-containing zwitterion 1048. Nearly ten analogs of these arylalkynyldibenzofurans having various substituents on the arenes coming from 1047 have been made and substituent perturbation on the absorption and emission spectra are being studied.
  • Pd-catalyzed cross couplings are effective for producing novel conjugated oligomers.
  • the bis-indanone adducts can also be exploited by converting them into: (i) the quasi-delocalized s-indacene derivatives (see 1053 and 1054) and (ii) bis-spirocyclic derivatives (see 1055).
  • These motifs have shown useful electro-optical behaviors, albeit for different reasons.
  • the 4n ⁇ electron count of the former brings interesting consequences to the redox and HOMO-LUMO gap properties.
  • the orthogonal bulk of the latter is believed to suppress excimer formation in solid films. Comparison of properties of the s- vs. the as- indacenes (cf.1053 vs.1054) will also be interesting.
  • Illustrative compounds that are planned to be made include the following.
  • benzocyclobutadiene 1038 have also been utilized. Substrates having only a two-atom linker between the diyne and diynophile typically do not undergo cyclization. Presumably, the resulting benzyne, housed within a benzocyclobutadiene motif, would be simply too strained. We recently hypothesized that we could use this situation to our advantage. A two-atom linker might allow cyclization to materialize, but only following initial benzyne formation in a substrate like 1056a (FIG.13A).
  • the intermediate benzyne 1056a Benz now has a nearby diyne whose proximal alkyne carbon is poised five, no longer four, atoms away (red dot and blue diamond in 1056 Benz ).
  • An initial experiment showed just that.
  • the acyclic ester-linked pentayne 1056a was smoothly converted to the hexacycle 1057a, in which a final intermediate naphthyne had been trapped (by furan). This represents an exciting new direction for this chemistry.
  • This domino- HDDA reaction was then extended to the homologous heptayne 1056b, which proceeds analogously to give 1057b.
  • arylalkynylfluoranthene derivative 1060 This is additionally noteworthy in view of the stabilizing influence that alkynyl substituents are known to impart on acenes.
  • the bridging oxygen atom in the furan-trapped adducts like 1057 and 1060 may be reductively removed to reveal an additional terminal benzo ring, adding to the acene length.
  • other traps as presented earlier in various different contexts, could be used to terminate the final domino acyne.
  • the homologous series of oligomeric acene products 1068 (as well as their precursors 1067) differ by having increasing numbers of orange subunits. A large amount of information about the properties of this homologous set of chromophoric structures can be obtained with a relatively small amount of overall effort. The preparation of large quantities of any one member of 1067 for device construction, would be feasible by the mid-chain coupling strategy (FIG.14A).
  • the iterative exponential growth (IEG) strategy recently revealed by the Jamison and Johnson groups was used to prepare the series of monodisperse, domino substrates 1069 (FIG.14D).
  • the starting material, 1069a (LLS 3), contains two orthogonally removable, terminal alkyne protecting groups.
  • This format is used to report 1 H resonances: chemical shift in ppm [multiplicity, coupling constant(s) (J) in Hz, integration to the nearest whole number of protons, and assignment].
  • 1 H NMR assignments are indicated by the substructure environment, e.g., OCH a H b . Some complex structures are numbered in order to simplify the proton assignment identification. Coupling constant analysis was guided by methods that have been previously reported.
  • HRMS High-resolution mass spectrometry
  • Propargyl bromide (7.8 mL, 80 wt. % in toluene, 70 mmol) was added to a stirred suspension of dimethyl malonate (2.00 mL, 17.5 mmol) and K 2 CO 3 (5.32 g, 38.5 mmol) in acetone (30 mL) under a N2 atmosphere. This mixture was brought to reflux (ca.60 o C). After 7 d the reaction mixture was filtered through Celite ® (acetone eluent) and concentrated. The residue was partitioned between water and EtOAc and the aqueous phase further extracted with EtOAc. The combined organic layers were washed with brine, dried (MgSO 4 ), and concentrated.
  • Powdered AgNO 3 (0.2 equiv) was added to a stirred solution of 4 (1.0 equiv) and N- bromosuccinimide (NBS, 2.4 equiv) in acetone (0.1 M) at room temperature. After 10 h the slurry was filtered through Celite® (acetone eluent) and concentrated. The residue was partitioned between water and EtOAc and the water layer was further extracted with EtOAc. The combined extracts were washed with brine, dried (MgSO 4 ), and concentrated.
  • the crude product was purified by flash chromatography (hexanes:EtOAc 7:1) to give the known tetrayne 99a (2.77 g, 6.8 mmol, 68%) (Zhang, H.; Hu, Q.; Li, L.; Hu, Y.; Zhou, P.; Zhang, X.; Xie, H.; Yin, F.; Hu, Y.; Wang, S. Chem. Commun.2014, 50, 3335–3337) as a pale yellow solid.
  • mp 96-98 °C (lit. value: 96–97 °C) (Zhang, H.; Hu, Q.; Li, L.; Hu, Y.; Zhou, P.; Zhang, X.; Xie, H.; Yin, F.; Hu, Y.; Wang, S. Chem. Commun.2014, 50, 3335–3337).
  • thermogravimetric analysis scan for 10a is seen in FIG.15A and the differential scanning calorimetry scan for 10a is seen in FIG.15B
  • thermogravimetric analysis scan for 10b is seen in FIG.16A and the differential scanning calorimetry scan for 10b is seen in FIG.16B.
  • FIG.16C shows a ORTEP rendering of the single crystal X-ray structure of 10b
  • thermogravimetric analysis scan for 10c is seen in FIG.17A and the differential scanning calorimetry scan for 10c is seen in FIG.17B.
  • FIGs.18A, 18B and 18C show the photoluminescence efficiency (solution quantum yield) for compounds 10a (FIG.18A), 10b (FIG.18B and 10c (Fig.18C) in THF/water mixtures.
  • FIGs.19A, 19B and 19C show electroluminescence for all nine devices including compound 10a (FIG.19A), 10b (FIG.19B) and 10c (FIG.19C) taken at 2 mA/cm 2 .
  • FIGs.20A show current-voltage and brightness-voltage data for compounds 10a in 4%, 20% and 100% UGH2 (FIG.20A, 20B and 20C respectively); 10b in 4%, 20% and 100% UGH2 (FIG.21A, 21B and 21C respectively); and 10c in 4%, 20% and 100% UGH2 (FIG. 22A, 22B and 22C respectively).

Abstract

L'invention concerne de nouveaux composés. De tels composés peuvent être synthétisés à l'aide d'une réaction d'hexadéhydro-Diels-Alder (HDD A). L'invention concerne également des dispositifs organiques comprenant un ou plusieurs composés décrits. Les dispositifs organiques peuvent comprendre des dispositifs électroniques organiques, des dispositifs photoniques organiques, ou des combinaisons de ceux-ci. Des types spécifiques de dispositifs peuvent comprendre, par exemple, des diodes électroluminescentes organiques (OLED), des dispositifs photovoltaïques organiques (OPV), des transistors organiques à effet de champ (OFET), ou des combinaisons de ceux-ci.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN110698332A (zh) * 2019-09-29 2020-01-17 桂林理工大学 一种四苯基乙烯炔苯基烷氧基桥接烷氧基苯并菲二元化合物及其制备方法
CN114874252A (zh) * 2022-06-06 2022-08-09 安徽师范大学 一种硅甲基萘衍生物及其制备方法和应用
WO2023052275A1 (fr) * 2021-09-28 2023-04-06 Merck Patent Gmbh Matériaux pour dispositifs électroniques

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US2230233A (en) * 1937-05-10 1941-02-04 Schering Corp Hydrogenated indane-diones and a method of producing the same
US20010011144A1 (en) * 2000-01-26 2001-08-02 Adchemco Corporation Preparation process of fluorenes
US20130197241A1 (en) * 2012-01-31 2013-08-01 Regents Of The University Of Minnesota Cyclization methods

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US2230233A (en) * 1937-05-10 1941-02-04 Schering Corp Hydrogenated indane-diones and a method of producing the same
US20010011144A1 (en) * 2000-01-26 2001-08-02 Adchemco Corporation Preparation process of fluorenes
US20130197241A1 (en) * 2012-01-31 2013-08-01 Regents Of The University Of Minnesota Cyclization methods

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110698332A (zh) * 2019-09-29 2020-01-17 桂林理工大学 一种四苯基乙烯炔苯基烷氧基桥接烷氧基苯并菲二元化合物及其制备方法
CN110698332B (zh) * 2019-09-29 2022-04-19 桂林理工大学 一种四苯基乙烯炔苯基烷氧基桥接烷氧基苯并菲二元化合物及其制备方法
WO2023052275A1 (fr) * 2021-09-28 2023-04-06 Merck Patent Gmbh Matériaux pour dispositifs électroniques
CN114874252A (zh) * 2022-06-06 2022-08-09 安徽师范大学 一种硅甲基萘衍生物及其制备方法和应用

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