CN104592491A - Naphthalene-based conjugated polymers and uses thereof - Google Patents

Naphthalene-based conjugated polymers and uses thereof Download PDF

Info

Publication number
CN104592491A
CN104592491A CN201310532879.XA CN201310532879A CN104592491A CN 104592491 A CN104592491 A CN 104592491A CN 201310532879 A CN201310532879 A CN 201310532879A CN 104592491 A CN104592491 A CN 104592491A
Authority
CN
China
Prior art keywords
preferred
base
alkyl
phenyl
polymkeric substance
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CN201310532879.XA
Other languages
Chinese (zh)
Other versions
CN104592491B (en
Inventor
韩续
梅建国
潘霄
张仲凝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Tachyon Amperex Technology Ltd
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to CN201310532879.XA priority Critical patent/CN104592491B/en
Publication of CN104592491A publication Critical patent/CN104592491A/en
Application granted granted Critical
Publication of CN104592491B publication Critical patent/CN104592491B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The present invention relates to the conjugated polymers and application thereof based on naphthalene, and more particularly to the polymer of formula 1a and 1b, wherein G1, G2, A1, A2, D1, D2, X, Y, m, n and q are defined as in the description. Also disclose the application of film and device and the polymer comprising formula 1a and 1b polymer in organic photovoltaic battery (OPVs).

Description

Based on the conjugated polymers and uses thereof of naphthalene
Technical field
The present invention relates to the conjugated polymers comprising the naphthalene monomer that 1,5-or 2,6-replaces, their preparation method, and they are in the purposes of organic photovoltaic battery (OPVs) as electron donor(ED).
Background technology
Photovoltaic cell (photovoltaics, PVs) is the sustainable energy solution of one helping to meet following ever-increasing energy requirement.Photovoltaic cell based on silicon materials is current business-like technology mainly, and its advantage is their high-energy conversion efficiency; But its shortcoming comprises high production cost and need process a large amount of wastes produced in preparation technology.Organic photovoltaic battery (organic photovoltaics, OPVs) is a kind of emerging technical solution scheme, can solve the problem of described high production cost and offal treatment.The preparation technology of OPVs, particularly adopts solution complete processing, has fast, the advantage of simple and easy and low cost, and is applicable to produce large-area flexible device.Summarize see Y.-J.Cheng etc., Chem.Rev.2009,109,5868.Wherein, body heterojunction (bulk heterojunction, BHJ) OPVs is a special class OPVs, its p-type electron donor material and N-shaped electron acceptor material blended in the photoactive layer of this battery; This kind of battery is widely studied, see G.Yu etc., Science1995, and 270,1789.
In OPVs field, usually expect that its electron donor material has narrower band gap (bandgap) and/or its device has higher open circuit voltage (open circuit voltage, V oc).The size of open circuit voltage is relevant to the energy level difference of the HOMO of the electron donor material of OPVs and the LUMO of its electron acceptor material.Because the space that relatively can change of the lumo energy of acceptor material is little, see such as, CN101483221B, it is generally acknowledged the open circuit voltage that will improve device, needs to research and develop novel electron donor material.
In order to effectively adjust energy level and the band gap thereof of HOMO and the LUMO of electron donor material, Optical Properties of Novel Conjugated just have employed has donor monomer and the scheme by body unit (D-A) simultaneously.Due to the donor monomer in conjugated polymers and by the Charger transfer between body unit be occur in same intramolecular, make the time shorten that its bond distance (list-double bond) converts, and along with the complanation of its main chain, thus improve the quantum yield of its charge separation.In addition, the HOMO of this conjugated polymers itself can be high than the HOMO of its donor monomer, and its LUMO can be low than its LUMO by body unit, just makes its band gap narrow.
Summary of the invention
The invention provides the polymkeric substance as shown in the formula 1a or 1b:
Wherein
G 1and G 2be selected from vinyl independently of one another, ethynyl, C 6-C 20substituted or unsubstituted arylidene and comprise 1,2 or 3 heteroatomic C independently selected from O, S and N 4-C 12substituted or unsubstituted heteroaryl;
A 1and A 2be selected from independently of one another
D 1and D 2be selected from independently of one another
X is C (O), C (S), C (O) O, or C (S) O;
Y is C 1-C 30alkyl, C 2-C 30thiazolinyl, C 3-C 20cycloalkyl, C 3-C 20cycloalkenyl group, C 4-C 30cycloalkylalkyl, C 4-C 30cycloalkenyl alkyl, C 2-C 20heterocyclic radical, C 3-C 30cycloheteroalkylalkyl, C 6-C 20aryl, or C 5-C 20heteroaryl;
Z is C 1-C 30alkyl, C 2-C 30thiazolinyl, C 3-C 20cycloalkyl, C 3-C 20cycloalkenyl group, C 4-C 30cycloalkylalkyl, C 4-C 30cycloalkenyl alkyl, C 2-C 20heterocyclic radical, C 3-C 30cycloheteroalkylalkyl, C 6-C 20aryl, or C 5-C 20heteroaryl;
Q is the integer of 1-3;
M is the integer of 5-100; With
N is the integer of 5-100.
In one embodiment, in polymkeric substance of the present invention, described G 1and G 2be selected from vinyl independently of one another, ethynyl, phenyl, xenyl, naphthyl, binaphthylyl, Azulene base, anthryl, naphthacenyl, base, pyrenyl, thienyl, thiophthene base, and thienothiophene base; Be preferably selected from phenyl, thienyl, thiophthene base and thienothiophene; Also be preferably thienyl.
In one embodiment, in polymkeric substance of the present invention, D 1and D 2m-1; X is C (O); Y is C 1-C 30alkyl, C 3-C 20cycloalkyl, C 4-C 30cycloalkylalkyl, C 2-C 20heterocyclic radical, or C 3-C 30cycloheteroalkylalkyl; And/or q is 1 or 2, be preferably 1.
In one embodiment, in polymkeric substance of the present invention, A 1and A 2be selected from Ar-1 independently of one another, Ar-3, and Ar-4; C with Z 1-C 30alkyl, C 3-C 20cycloalkyl, C 4-C 30cycloalkylalkyl, C 2-C 20heterocyclic radical, or C 3-C 30cycloheteroalkylalkyl.
In one embodiment, polymkeric substance of the present invention is poly-{ (E)-6-(5-(4, two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) naphthalene-2-base of 8-) thiophene-2-base)-1, 1 '-bis-(2-hexyl decyl)-[3, 3 '-bis-(indolylidene)]-2, 2 '-diketone } (i.e. PT4NIsoI), poly-{ 1, 1'-(5, 5'-(3-(5-(benzo [c] [1, 2, 5] thiadiazoles-4-base) thiophene-2-base)-7-(thiophene-2-base) naphthalene-1, 5-bis-base) two (thiophene-5, 2-bis-base)) two (2-hexyl-1-in last of the ten Heavenly stems ketone) } (i.e. PT4NBTD), or poly-{ 1-(5-(4, two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) naphthalene-2-base of 8-) thiophene-2-base)-5-octyl group-4H-thieno-[3, 4-c] pyrroles-4, 6 (5H)-diketone } (i.e. PT4NTPD).
The present invention also provides the polymkeric substance of contained 1a or 1b to be used as the film of electron donor material, and its thickness is about 1 nanometer-Yue 1000 nanometer.
The present invention further provides and comprise anode, the device of negative electrode and photoactive layer, wherein said photoactive layer comprises the polymkeric substance of described formula 1a or 1b, and its thickness is about 1 nanometer-about 1000 nanometers.
In addition, the present invention also provides the purposes of polymkeric substance for organic photovoltaic battery of formula 1a or 1b, and the polymkeric substance of wherein said formula 1a or 1b is used as electron donor material.
Accompanying drawing explanation
Exemplaryly better can understand the present invention by reference to the accompanying drawings:
Fig. 1. formula 1a polymer P T4NIsoI is in chloroformic solution and in solid-state optical characteristics.
Fig. 2. formula 1a polymer P T4NBTD is in chloroformic solution and in solid-state optical characteristics.
Fig. 3. formula 1a polymer P T4NTPD is in chloroformic solution and in solid-state optical characteristics.
Fig. 4. containing formula 1a polymer P T4NIsoI/PC 71the BHJ device of BM, with simulated solar irradiation, is 100mW/cm in intensity 2j-V curve under irradiating.
Fig. 5. containing formula 1a polymer P T4NBTD/PC 71the BHJ device of BM, with simulated solar irradiation, is 100mW/cm in intensity 2j-V curve under irradiating.
Fig. 6. containing formula 1a polymer P T4NTPD/PC 61the BHJ device of BM, with simulated solar irradiation, is 100mW/cm in intensity 2j-V curve under irradiating.
Embodiment
Unless otherwise indicated, all publications that the present invention mentions, patent application, patent and other reference are incorporated into herein all by reference in full, are equivalent to be presented in herein in full.
Unless otherwise defined, all technology used herein and scientific terminology have usual the understood same implication of one skilled in the art of the present invention.When inconsistent or conflict, be as the criterion with the definition of this specification sheets.
When with scope, preferable range, or the form of preferred numerical upper limits and preferred numerical lower limits states certain amount, when concentration or other value or parameter, be to be understood that and be equivalent to specifically disclose any scope by any pair range limit or preferred value being combined with any range lower limit or preferred value, and do not consider whether this scope specifically discloses.Unless otherwise noted, numerical range listed herein is intended to the end points comprising scope, and all integers within this scope and mark.
Term used herein " comprises ", " comprising ", " having ", and " having " " is contained " or their other variants any, is comprising of intention statement non-exclusionism.Such as, comprise the composition of a series of key element, process, method, device or equipment might not be only limited to those key elements, but can also comprise clearly do not list or these compositions, process, method, device or intrinsic other key elements of equipment.
Term " by ... composition " do not comprise any key element clearly do not enumerated, step or composition.If there is in the claims, such term does not comprise making claim be limited to described material the material do not described, but still comprises the impurity usually relevant to described material.When term " by ... composition " appears at the characteristic of claim, but not immediately preamble time, it is only limitted to the key element set forth in characteristic; Other key element is not got rid of by from this claim entirety.
Term " comprise " intention contain term " substantially by ... composition " and " by ... form " included by embodiment.Similarly, term " substantially by ... composition " intention comprise term " by ... composition " included by embodiment.
When parameter is with scope, preferable range, or a series of upper limit preferred value and lower preferable values limit Range Representation time, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope has carried out open separately.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
When term " about " is used to the end value describing numerical value or scope, describedly its concrete numerical value related to or end value openly should be understood to include.
In addition, contrary unless expressly stated, otherwise "or" refers to the "or" of inclusive but not exclusive "or".Such as, any condition A or B:A that satisfy condition is true (or existence) and B is false (or not existing) below, A is false (or not existing) and B is true (or existence), and A and B is true (or existence).
In the foregoing description, in substituting group the sum of carbon atom by prefix " C i-C j" represent, wherein i and j is the numerical value of 1 to 30.
In one embodiment, term " alkyl ", when being used alone or as another group a part of, refers to " C 1to C 30alkyl ", and refer to saturated hydrocarbyl that is linear or branching.The example of alkyl includes but not limited to, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, tert-pentyl and hexyl.Preferred alkyl comprises 6 to 24 carbon atom (C 6to C 24alkyl).Preferred alkyl comprises 10 to 20 carbon atom (C 10to C 20alkyl).Similarly, thiazolinyl refers to linear in double bond containing unsaturated alkyl that is branching.The example of thiazolinyl includes but not limited to, vinyl, allyl group, butenyl etc.Preferred thiazolinyl comprises 2 to 24 carbon atom (C 2to C 24thiazolinyl).Preferred thiazolinyl bag 10 to 20 carbon atom (C 10to C 20thiazolinyl).
Alkyl can be unsubstituted, or is replaced by one or more substituting group.Described substituting group is selected from halogen, hydroxyl, acyl group, acyloxy, nitro, carboxyl, formamyl, amide group, cyano group, alkylsulfonyl, sulfonamido, sulfinyl, sulfonamido, thiol group, alkylthio or alkyl sulphonyl.Any substituting group can be unsubstituted, or is replaced by above-mentioned arbitrary substituting group further.
Herein term " cycloalkyl " be used alone or as another group a part of time, refer to " C 3to C 30cycloalkyl ", and refer to saturated monocycle or polycyclic moiety.The limiting examples of cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, two rings [2.2.1] heptyl, two rings [2.2.2] octyl group or adamantyl.Similarly, cycloalkenyl group refers to " C 3to C 20cycloalkenyl group ", and be the double bond containing unsaturated alkyl of monocycle or many rings.The example of cycloalkenyl group comprises cyclopentenyl, cyclohexenyl etc.Preferred cycloalkenyl group comprises 3 to 16 carbon atom (C 3to C 16cycloalkenyl group).Preferred cycloalkenyl group comprises 3 to 12 carbon atom (C 3to C 12cycloalkenyl group).Cycloalkyl or cycloalkenyl group can be unsubstituted, or are replaced by one or more substituting group, described substituting group as the above-mentioned substituting group to alkyl define.
Term " C herein 2-C 20heterocyclic radical " be used alone or as another group a part use time, represent there is 1 to 4 heteroatomic ternary to octatomic ring, described heteroatoms is as oxygen, and sulphur and/or nitrogen, it comprises 1 to 20 carbon atom.These ternarys to octatomic ring can be saturated, completely undersaturated or part is undersaturated.The limiting examples of heterocycle comprises Oxyranyle (oxiranyl), oxetanyl, piperidyl, pyrrolidyl, pyrrolinyl, pyrazolinyl, pyrazolidyl, morpholinyl, thio-morpholinyl, pyranyl, thiopyranyl, piperazinyl, indyl, dihydrofuran base, tetrahydrofuran base, dihydro-thiophene base, tetrahydro-thienyl, dihydro pyranyl, THP trtrahydropyranyl etc.Heterocyclic radical can be unsubstituted, or by available atom by one or more as above-mentioned to alkyl the group that limits replace.
Term " C herein 4-C 30cycloalkylalkyl " be the alkyl be substituted by cycloalkyl, it comprises 4 to 30 carbon atoms; More clearly, refer to by C 3-C xthe C of cycloalkyl substituted 1-C (30-x)alkyl.Similarly, term " C 4-C 30cycloalkenyl alkyl " refer to the alkyl replaced by cyclenes alkyl, it comprises 4 to 30 carbon atoms.Term " C 3-C 30cycloheteroalkylalkyl " alkyl that replaced by Heterocyclylalkyl, it comprises 3 to 30 carbon atoms.As an example, " oxiranylmethyl radical " is exactly a kind of C 3heterocyclic radical.
Herein term " aryl " and be used alone or as another group a part of time, refer to the aromatic ring system containing 6-20 ring carbons.Aryl rings can be monocycle, dicyclo, three rings or Fourth Ring etc.The limiting examples of aryl is phenyl, xenyl, and naphthyl comprises 1-naphthyl and 2-naphthyl etc.Aryl can be unsubstituted or by the carbon atom that can be substituted by one or more as above-mentioned to alkyl the group that limits replace." aralkyl " represents the aryl (such as benzyl) being bonded to alkyl.Similarly, term " arylidene " refers to divalent aryl, and as defined above, wherein aryl is connected with two other groups difference bondings on two positions.
Herein term " heteroaryl " be used alone or as another group a part of time, represent that comprising at least one annular atoms is heteroatomic heteroaromatic system, described heteroatoms is selected from nitrogen, sulphur and oxygen.Heteroaryl comprises 5 or more ring member nitrogen atoms.Heteroaryl can be monocycle, dicyclo, three rings etc.Heteroaryl also comprises benzheterocycle.If nitrogen is ring member nitrogen atoms, the present invention also comprises the heteroaryl of nitrogenous N-oxide compound.The limiting examples of heteroaryl comprises thiophene, thionaphthene, 1-aphthothiophenes, thianthrenyl, furyl, benzofuryl, pyrryl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indyl, pseudoindoyl, indazolyl, purine radicals, isoquinolyl, quinolyl, naphthyridinyl, quinoxalinyl, quinazolyl, cinnolines base, pteridine radicals (pteridinyl), carbolinyl, thiazolyl ， oxazolyl, isothiazolyl ， isoxazolyl etc.Heteroaryl can be unsubstituted or by the atom that can be substituted by one or more as above-mentioned to alkyl the group that limits replace.
During the structure of outlines device in this article, use " // " to separate different functional layers, use "/" to carry out point stacked film with unlike material be interposed between in same functional layer, use ": " to show differing materials mixed in same functional layer.
In this article, the negative pole (cathode) of organic solar batteries is negative electrode, and it obtains electronics by photoactive layer, and reduction reaction occurs; Positive pole (anode) is then anode, and it obtains hole by photoactive layer, and oxidizing reaction occurs.Its definition is that those of ordinary skill in the art are usual understood.
Embodiment of the present invention comprise, such as:
The polymkeric substance of embodiment 1A. formula 1a or 1b, wherein G 1and G 2be selected from vinyl independently of one another, ethynyl, C 6-C 20substituted or unsubstituted arylidene and comprise 1,2 or 3 heteroatomic C independently selected from O, S and N 4-C 12substituted or unsubstituted heteroaryl.
The polymkeric substance of embodiment 1B. embodiment 1A, wherein G 1and G 2be selected from vinyl independently of one another, ethynyl, C 6-C 20unsubstituted arylidene and comprise 1,2 or 3 heteroatomic C independently selected from O, S and N 4-C 12unsubstituted heteroaryl.
The polymkeric substance of embodiment 1C. embodiment 1B, wherein G 1and G 2it is the heteroaryl comprising 1 or 2 S atom.
The polymkeric substance of embodiment 1D. embodiment 1A, wherein G 1and G 2be selected from vinyl independently of one another, ethynyl, phenyl, xenyl, naphthyl, binaphthylyl, Azulene base, anthryl, naphthacenyl, base, pyrenyl, thienyl, thiophthene base, and thienothiophene base.
The polymkeric substance of embodiment 1E. embodiment 1D, wherein G 1and G 2be selected from phenyl independently of one another, thienyl, thiophthene base, and thienothiophene base.
The polymkeric substance of embodiment 1F. embodiment 1E, wherein G 1and G 2it is thienyl.
The polymkeric substance of embodiment 2A. formula 1a or 1b, wherein A 1and A 2be selected from Ar-1 independently of one another, Ar-2, Ar-3, Ar-4, and Ar-5.
The polymkeric substance of embodiment 2B. embodiment 2A, wherein A 1and A 2be selected from Ar-1 independently of one another, Ar-3, and Ar-4.
The polymkeric substance of embodiment 2C. embodiment 2B, wherein A 1and A 2ar-3.
The polymkeric substance of embodiment 3A. formula 1a or 1b, wherein D 1and D 2m-1, M-2, or M-3.
The polymkeric substance of embodiment 3B. embodiment 3A, wherein D 1and D 2m-1.
The polymkeric substance of embodiment 3C. embodiment 3B, wherein D 1and D 2it is 2,5-thienyl.
The polymkeric substance of embodiment 4A. formula 1a or 1b, wherein X is C (O), C (S), C (O) O, or C (S) O.
The polymkeric substance of embodiment 4B. embodiment 3A, wherein X is C (O) or C (S).
The polymkeric substance of embodiment 4C. embodiment 3B, wherein X is C (O).
The polymkeric substance of embodiment 5A. formula 1a or 1b, wherein Y is C 1-C 30alkyl, C 2-C 30thiazolinyl, C 3-C 20cycloalkyl, C 3-C 20cycloalkenyl group, C 4-C 30cycloalkylalkyl, C 4-C 30cycloalkenyl alkyl, C 2-C 20heterocyclic radical, C 3-C 30cycloheteroalkylalkyl, C 6-C 20aryl, or C 5-C 20heteroaryl.
The polymkeric substance of embodiment 5B. embodiment 5A, wherein Y is C 6-C 24alkyl, C 6-C 24thiazolinyl, C 3-C 16cycloalkyl, C 3-C 16cycloalkenyl group, C 4-C 24cycloalkylalkyl, C 4-C 24cycloalkenyl alkyl, C 2-C 14heterocyclic radical, C 3-C 22cycloheteroalkylalkyl, C 6-C 16aryl, or C 5-C 16heteroaryl.
The polymkeric substance of embodiment 5C. embodiment 5B, wherein Y is C 10-C 20alkyl, C 10-C 20thiazolinyl, C 3-C 12cycloalkyl, C 3-C 12cycloalkenyl group, C 4-C 20cycloalkylalkyl, C 4-C 20cycloalkenyl alkyl, C 3-C 10heterocyclic radical, C 3-C 18cycloheteroalkylalkyl, C 6-C 12aryl, or C 5-C 12heteroaryl.
The polymkeric substance of embodiment 5D. embodiment 5A, wherein Y is C 1-C 30alkyl, C 3-C 20cycloalkyl, C 4-C 30cycloalkylalkyl, C 2-C 20heterocyclic radical, or C 3-C 30cycloheteroalkylalkyl.
The polymkeric substance of embodiment 5E. embodiment 5D, wherein Y is C 1-C 30alkyl, C 4-C 30cycloalkylalkyl, or C 3-C 30cycloheteroalkylalkyl.
The polymkeric substance of embodiment 5F. embodiment 5E, wherein Y is C 1-C 30alkyl, preferred C 6-C 24alkyl, also preferred C 10-C 20alkyl.
The polymkeric substance of embodiment 6A. formula 1a or 1b, wherein Z is C 1-C 30alkyl, C 2-C 30thiazolinyl, C 3-C 20cycloalkyl, C 3-C 20cycloalkenyl group, C 4-C 30cycloalkylalkyl, C 4-C 30cycloalkenyl alkyl, C 2-C 20heterocyclic radical, C 3-C 30cycloheteroalkylalkyl, C 6-C 20aryl, or C 5-C 20heteroaryl.
The polymkeric substance of embodiment 6B. embodiment 6A, wherein Z is C 6-C 24alkyl, C 6-C 24thiazolinyl, C 3-C 16cycloalkyl, C 3-C 16cycloalkenyl group, C 4-C 24cycloalkylalkyl, C 4-C 24cycloalkenyl alkyl, C 2-C 14heterocyclic radical, C 3-C 22cycloheteroalkylalkyl, C 6-C 16aryl, or C 5-C 16heteroaryl.
The polymkeric substance of embodiment 6C. embodiment 6B, wherein Z is C 10-C 20alkyl, C 10-C 20thiazolinyl, C 3-C 12cycloalkyl, C 3-C 12cycloalkenyl group, C 4-C 20cycloalkylalkyl, C 4-C 20cycloalkenyl alkyl, C 3-C 10heterocyclic radical, C 3-C 18cycloheteroalkylalkyl, C 6-C 12aryl, or C 5-C 12heteroaryl.
The polymkeric substance of embodiment 6D. embodiment 6A, wherein Z is C 1-C 30alkyl, C 3-C 20cycloalkyl, C 4-C 30cycloalkylalkyl, C 2-C 20heterocyclic radical, or C 3-C 30cycloheteroalkylalkyl.
The polymkeric substance of embodiment 6E. embodiment 6D, wherein Z is C 1-C 30alkyl, C 4-C 30cycloalkylalkyl, or C 3-C 30cycloheteroalkylalkyl.
The polymkeric substance of embodiment 6F. embodiment 6E, wherein Z is C 1-C 30alkyl, preferred C 6-C 24alkyl, also preferred C 10-C 20alkyl.
The polymkeric substance of embodiment 7. formula 1a or 1b, wherein q is the integer of 1-3, is preferably 1 or 2, is also preferably 1.
The polymkeric substance of embodiment 8. formula 1a, wherein m is the integer of 5-100, preferably 8-60.
The polymkeric substance of embodiment 9. formula 1b, wherein n is the integer of 5-100, preferably 8-60.
Generally speaking, embodiment disclosed herein is only exemplary, and should be understood as the present invention and can be embodied in many differences and alternative form.Therefore, ad hoc structure disclosed herein and functional details should not be construed as restrictive, and only as the basis of claim, and implement representative basis of the present invention as instruction those skilled in the art with different schemes.Described by summary of the invention part, embodiment of the present invention comprise other embodiment any described herein, can combine by any way.
The polymkeric substance of formula 1a by the method as shown in following route 1-15 and can slightly make the method preparation changed.In the polymkeric substance of following formula 1a and the compound of formula 2a-18a, wherein A 1, G 1, D 1, the definition of X and Y respectively as in aforementioned " summary of the invention " part define, except as otherwise noted; R 1, R 2, R 3and R 4definition then describe in detail in hereafter relevant routes.
In addition, those skilled in the art can also know and recognize easily, to consider between polymkeric substance 1b and 1a clearly spatial correspondence, by selecting 2,6-dihydroxy naphthlene (CAS 581-43-1), as parent material, can adopt the method that is similar to preparation formula 1a polymkeric substance and/or slightly make the method that changes to prepare polymkeric substance 1b.
In one embodiment, as as shown in route 1, the polymkeric substance of formula 1a can the compound of through type 2a and the compound of formula 3a virtueization linked reaction (directheteroarylation) of carrying out directly mixing be prepared, and the compound of its Chinese style 2a has two halogen functional group.Described halogen is chlorine, bromine or iodine, is preferably bromine.It should be noted that A 1be preferably thieno-[3,4-c] pyrroles-4,6-dione unit (i.e. Ar-1), 2,1,3-diazosulfide unit (i.e. Ar-3), or (3,3'-pair-indoline)-2,2'-dione units (having another name called isoindigo, i.e. Ar-4).
Described reaction, can in various suitable solvent under existing containing Phosphine ligands and alkali at palladium catalyst, and the reaction preferably carried out at 50 DEG C-150 DEG C 1-24 hour carrys out the polymkeric substance of preparation formula 1a.The example of described palladium catalyst includes but not limited to Pd (II) (OAc) 2.The described example containing Phosphine ligands includes but not limited to PPh 3, P (p-PhCH 3) 3, P (o-PhOCH 3) 3, P (cyclo-C 6h 12) 3-HBF 4and/or P (t-Bu) 2cH 3-HBF 4deng.The example of described alkali includes but not limited to salt of wormwood or cesium carbonate.Described solvent includes but not limited to tetrahydrofuran (THF) (THF), toluene, dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc) or its mixture.After this reaction terminates, the reaction mixture of gained usually after filtration with purify to remove remaining catalyzer and low molecular weight product, and the final formula 1a polymkeric substance obtaining number-average molecular weight and be at least greater than 7kD.For this direct assorted virtueization linked reaction, can see P.Berrouard etc., Angew.Chem.Int.Ed.2012,51,2068 and the reference wherein quoted.
route 1
Wherein, Hal is Cl, Br or I.
In another embodiment, as shown in route 2, the polymkeric substance of formula 1a also can the compound of through type 4a and the compound of formula 5a virtueization linked reaction of carrying out directly mixing be prepared, and wherein, the compound of formula 5a has two halogen functional group.Described halogen is chlorine, bromine or iodine, is preferably bromine.It should be noted that A 1preferably thieno-[3,4-c] pyrroles-4,6-dione unit (i.e. Ar-1), 2,1,3-diazosulfide unit (i.e. Ar-3), or (3,3'-pair-indoline)-2,2'-dione units (having another name called isoindigo, i.e. Ar-4).
Described reaction, can in various suitable solvent under existing containing Phosphine ligands and alkali at palladium catalyst, and the reaction preferably carried out at 50 DEG C-150 DEG C 1-24 hour carrys out the polymkeric substance of preparation formula 1a.The example of described palladium catalyst includes but not limited to Pd (II) (OAc) 2.The described example containing Phosphine ligands includes but not limited to PPh 3, P (p-PhCH 3) 3, P (o-PhOCH 3) 3, P (cyclo-C 6h 12) 3-HBF 4and/or P (t-Bu) 2cH 3-HBF 4deng.The example of described alkali includes but not limited to salt of wormwood or cesium carbonate.Described solvent includes but not limited to tetrahydrofuran (THF), toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE or its mixture.After this reaction terminates, the reaction mixture of gained usually after filtration with purify to remove remaining catalyzer and low molecular weight product, and the final formula 1a polymkeric substance obtaining number-average molecular weight and be at least greater than 7kD.
route 2
Wherein, Hal is Cl, Br or I.
In yet another embodiment, as shown in route 3, the polymkeric substance of formula 1a the compound of through type 5a and the compound of formula 6a can carry out Suzuki and reacts to prepare.Wherein, the compound of formula 6a has two R 1functional group, wherein R 1for boronate (B (OH) 2) or boric acid alkoxy (i.e. B (OR) 2, wherein OR is alkoxyl group, preferred C 1-C 6alkoxyl group), and preferred R 1for boric acid connection tetramethyl ethylene ketone base).
Suzuki reaction is extensively known in chemical literature.Usually, at palladium catalyst (such as, three (dibenzalacetone) two palladium (0) (Pd 2(dba) 3, CAS 51364-51-3), two (dibenzalacetone) palladium (0) (Pd (dba) 2, CAS 32005-36-0), or tetrakis triphenylphosphine palladium (0) (Pd (PPh 3) 4, CAS 14221-01-3)), containing Phosphine ligands (such as, P (o-PhOCH 3) 3), and the reaction under alkali (such as, salt of wormwood or cesium carbonate) existence can, in various suitable solvent, utilize the temperature (from room temperature to solvent reflux temperature) optimized to carry out 6-48 hour under air-proof condition.Described solvent comprises tetrahydrofuran (THF), toluene, dimethyl formamide, glycol dimethyl ether (dimethoxyethane), or its mixture.The solvability of initial reactant is looked in this reaction, sometimes can add appropriate water and other solvent use.After this reaction terminates, gained reaction mixture usually after filtration with purify to remove remaining catalyzer and low molecular weight product, and the final formula 1a polymkeric substance obtaining number-average molecular weight and be at least greater than 7kD.Polyreaction is carried out for use Suzuki linked reaction, can see W.Li etc., J.Am.Chem.Soc.2012,134,13787 and the reference wherein quoted.
route 3
Wherein, Hal is Cl, Br or I; R 1b (OH) 2or B (OR) 2.
In another embodiment, as shown in route 4, the polymkeric substance of formula 1a also the compound of through type 2a and the compound of formula 7a can carry out Suzuki and reacts to prepare, and wherein, the compound of formula 7a has two R 1functional group, wherein R 1for boronate or boric acid alkoxy, described alkoxyl group is preferably C 1-C 6alkoxyl group, and preferred R 1for boric acid connection tetramethyl ethylene ketone ester group.Usually, at palladium catalyst (such as, three (dibenzalacetone) two palladium (0), two (dibenzalacetone) palladium (0), or tetrakis triphenylphosphine palladium (0)), containing Phosphine ligands (such as, three (2-p-methoxy-phenyl) phosphine (P (o-PhOCH 3) 3cAS 4731-65-1)), the temperature of optimization (reflux temperature from room temperature to reaction mixture) can be utilized in various suitable solvent under air-proof condition to carry out 6-48 hour with the reaction under alkali (such as, salt of wormwood or cesium carbonate) exists.Described solvent comprises tetrahydrofuran (THF), toluene, dimethyl formamide, glycol dimethyl ether, or its mixture.The solvability of initial reactant is looked in this reaction, sometimes can add appropriate water and other solvent use.After this reaction terminates, gained reaction mixture usually after filtration with purify to remove remaining catalyzer and low molecular weight product, and the final formula 1a polymkeric substance obtaining number-average molecular weight and be at least greater than 7kD.
route 4
Wherein, Hal is Cl, Br or I; R 1b (OH) 2or B (OR) 2.
As shown in route 5, the compound of formula 7a can by the compound of formula 3a and (alkoxyl group) two boron (B 2(OR) 4) react and prepare (such as, connection pinacol borate, CAS 73183-34-3).Usually, G in formula 3a compound 1on hydrogen atom by the catalysis of metal catalyst, in various suitable solvent and at the temperature (reflux temperature from room temperature to reaction mixture) optimized, carry out just can being substituted and generating the formula 7a compound with boric acid alkoxy for 6-24 hour.Described transition-metal catalyst is preferably iridium catalyst, such as, and (1,5-cyclooctadiene) (methoxyl group) iridium (I) dimer ([Ir (OCH 3) (C 8h 12)] 2, CAS 12148-71-9).After this reaction terminates, the reaction mixture of gained usually after filtration with purify to remove unnecessary (alkoxyl group) two boron and relict catalyst.For use connection pinacol borate, can see J.Takagi etc., TetrahedronLetters, 2002,43 (32), 5649 and the reference wherein quoted.
route 5
As shown in route 6, the compound of formula 5a can be reacted by the compound of formula 3a and halogenating agent and be prepared (such as, N-bromine succinimide (NBS, CAS 128-08-5), N-chloro-succinimide (NCS, CAS 128-09-6), N-iodine succinimide (NIS, CAS 516-12-1), or Br 2).Usually, G in formula 3a compound 1on hydrogen atom at various suitable solvent (such as, dimethyl formamide or chloroform) neutralization optimize temperature (room temperature is to solvent reflux temperature) under, carry out just to be generated the formula 5a compound with two halogen functional group by halo in 1-24 hour.After this reaction terminates, the reaction mixture of gained is usually through precipitating and purifying to remove unnecessary halogenating agent and impurity.For use halogenating agent, can see A.Tamayo etc., J.Phys.Chem.C, 2008,112,11547 and the reference wherein quoted.
route 6
As shown in route 7, the compound of formula 3a can be reacted by the compound of the compound of formula 8a and formula 9a and be prepared.Wherein, the R on formula 8a compound 1for boronate or boric acid alkoxy; And the R on formula 9a compound 2be defined as sulfonate group, and be preferably trifluoromethanesulfonic acid ester group.Described reaction utilizes palladium catalyst (such as, three (dibenzalacetone) two palladium (0), two (dibenzalacetone) palladium (0), or tetrakis triphenylphosphine palladium (0)) and alkali (such as, salt of wormwood or ammonium hydroxide) exist under, in various suitable solvent, the temperature (reflux temperature from room temperature to reaction mixture) optimized is utilized to carry out 1-24 hour.After question response terminates, gained reaction mixture usually after filtration with purification to remove unnecessary start material and relict catalyst.For this reaction, can see Z.Xue etc., Macromolecules2010,43,9277 and the reference wherein quoted.
route 7
As shown in route 8, the compound of formula 8a can by the compound of formula 10a and (alkoxyl group) two boron at iridium catalyst, such as, there is lower reaction preparation 1-24 hour in (1,5-cyclooctadiene) (methoxyl group) iridium (I) dimer.After question response terminates, gained mixture usually after filtration with purify to remove unnecessary (alkoxyl group) two boron and relict catalyst.In route 8, described (alkoxyl group) two boron preferably use connection pinacol borate.Pertinent literature is as described in route 5.
route 8
As shown in route 9, by the compound of the compound of formula 11a and formula 12a at palladium catalyst, can there is lower reaction realization containing Phosphine ligands and alkali in the preparation of the compound of formula 10a.Halogen functional group in formula 11a is chlorine, bromine or iodine, is preferably chlorine.Described reaction under condition of no solvent, or can carry out about 1-24 hour in various suitable solvent.The temperature of described reaction can be the reflux temperature from room temperature to 200 DEG C or reaction mixture, preferably at 50 DEG C-150 DEG C.Described solvent includes but not limited to tetrahydrofuran (THF) or toluene.After question response terminates, the reaction mixture of gained usually after filtration with purify to remove unnecessary start material and remaining catalyzer.
route 9
Wherein, Hal is Cl, Br or I.
As shown in route 10, the preparation of the compound of formula 11a can be realized by the reaction of the compound of formula 13a and thionyl halide.The halogen functional group of thionyl halide used is chlorine, bromine or iodine, is preferably chlorine.Be the reaction of acyl halide (such as chloride of acid) by Carboxylic Acid be well-known to those skilled in the art, this reaction solvent-free or in various suitable solvent, can carry out about 1-24 hour from 0 DEG C to 150 DEG C.Described solvent comprises methylene dichloride, tetrahydrofuran (THF) or toluene etc., and the compound of a solemnity 13a can dissolve wherein.For this reaction, can see C.F.H.Allen etc., Organic Syntheses1963,4,739.
route 10
Wherein, Hal is Cl, Br or I.
As shown in route 11, the preparation of the compound of formula 9a can by the compound of formula 14a and sulphonic acid anhydride, alkali, and in various suitable solvent, reaction realizes.Described sulphonic acid anhydride is preferably trifluoromethanesulfanhydride anhydride (CAS 358-23-6).Described solvent includes but not limited to tetrahydrofuran (THF), toluene, methylene dichloride or its mixture.Described sulfonation reaction can carry out about 1-24 hour at 0 DEG C to room temperature condition.After reaction, gained reaction product obtains the product of high purity formula 9a by purifying.
route 11
Wherein, R 2for sulfonate group.
As shown in route 12, the preparation of the compound of formula 14a by the compound of formula 15a in various suitable solvent, can be carried out reaction with acid or alkali and realizes.In the compound of formula 15a, R 3protected hydroxy functional group (such as, 2-oxygen base-cyclohexene oxide groups).According to protection functional group used, acid can be added or alkali carrys out catalysis deprotection reaction in suitable solvent.Described solvent includes but not limited to tetrahydrofuran (THF), toluene, methylene dichloride or its mixture.Usually, described deprotection reaction can carry out about 1-24 hour at room temperature to 100 DEG C.
In one embodiment, in the compound of formula 15a, R 3be 2-oxygen base-cyclohexene oxide groups, and described deprotection reaction preferably carry out in hydrochloric methanol solution.
route 12
As shown in route 13, the compound of formula 15a can carry out Suzuki by the compound of the compound of formula 16a and formula 17a and react to prepare.Wherein, the compound of formula 16a has a halogen functional group.Described halogen is chlorine, bromine or iodine, is preferably bromine.In addition, the compound of formula 17a has two R 3with two R 4functional group, wherein, R 3protected hydroxy functional group, such as, 2-oxygen base-cyclohexene oxide groups; And R 4for boronate (B (OH) 2) or boric acid alkoxy (i.e. B (OR) 2, wherein OR is alkoxyl group, preferred C 1-C 6alkoxyl group), and preferred R 4for boric acid connection tetramethyl ethylene ketone base.Suzuki reaction is being shown above, also can see above-mentioned reference.
route 13
Wherein, Hal is Cl, Br or I.
As shown in route 14, the compound of formula 17a can by the compound of formula 18a and (alkoxyl group) two boron react and prepare.Reaction conditions, method of purification and pertinent literature are as described in route 5.In the compound of formula 18a, R 3it is protected hydroxy functional group.
route 14
As shown in route 15, the compound of formula 18a can be prepared by 1,5-dihydroxy naphthlene and the suitable reagent react with protection hydroxy functional group.According to selected reagent, can add acid or alkali to the speed adding fast response and carry out with improve productive rate.For protection hydroxyl functional group selection with use be synthetic chemistry field technician known by; see T.W.Greene; and P.G.M.Wuts; Protective Groups in Organic Synthesis; the second edition, JohnWiley & Sons, Inc.; NewYork, 1991.Particularly the chapter 3 summary of this book is for the protection of the hydroxyl of phenol compound and the multiple method of deprotection.
In one embodiment, the compound of described formula 18a is prepared by the reaction between 3,4-dihydro-2H-pyrans and 1,5-dihydroxy naphthlene, i.e. R 3it is 2-oxygen base-cyclohexene oxide groups.About use 3,4-dihydro-2H-pyrans, the hydroxyl of two on naphthalene nucleus is protected, can see G.Maity etc., Synthetic Communications1993,23,1667.The reaction product of gained, by purification step, comprises saturated sodium bicarbonate solution washing, solvent extraction and recrystallization and obtain the compound of purified formula 18a.
route 15
Wherein, R 3it is protected hydroxy functional group.
In addition, present invention also offers film, its polymkeric substance comprising formula 1a of the present invention or 1b is as electron donor material.The thickness of described film is about 1 nanometer-about 1000 nanometers.Preferably the thickness of this film is not less than about 10 nanometers, or is not less than about 50 nanometers, and/or the thickness of preferred this film is not higher than about 500 nanometers, or not higher than about 250 nanometers.
In one embodiment, the thickness of described film is about 1 nanometer-about 1000 nanometers, and preferably this thickness is not less than about 50 nanometers, or is not less than about 80 nanometers, and/or preferably this thickness not higher than about 500 nanometers, or not higher than about 200 nanometers.
Described film of the present invention comprises electron acceptor material further.The described electron acceptor material be applicable in film of the present invention comprises the common electron acceptor material in this area.Such as, fullerene derivate, such as [6,6]-phenyl-C 61methyl-butyrate (PC 61bM, CAS:160848-22-6), [6,6]-phenyl-C 71methyl-butyrate (PC 71bM, CAS:609771-63-3), [6,6]-phenyl-C 85methyl-butyrate ([84] PCBM, CAS:905843-95-0), [6,6]-phenyl-C 61butyl butyrate (PCBB, CAS:571177-66-7), indenes-C 60two adductss (ICBA, CAS:1207461-57-1); Be preferably PC 61bM or PC 71bM.See J.C.Hummelen etc., J.Org.Chem.1995,60,532.
In one embodiment, film of the present invention comprises electron acceptor material further.
In one embodiment, in described film, described electron acceptor material is selected from [6,6]-phenyl-C 61methyl-butyrate (PC 61bM, CAS:160848-22-6), [6,6]-phenyl-C 71methyl-butyrate (PC 71bM, CAS:609771-63-3), [6,6]-phenyl-C 85methyl-butyrate ([84] PCBM, CAS:905843-95-0), [6,6]-phenyl-C 61butyl butyrate (PCBB, CAS:571177-66-7), indenes-C 60two adductss (ICBA, CAS:1207461-57-1); Be preferably PC 61bM or PC 71bM.
Present invention also offers and comprise anode, the device of negative electrode and photoactive layer, wherein said photoactive layer comprises the polymkeric substance of formula 1a or 1b.Generally speaking, in organic photovoltaic battery, the thickness of its photoactive layer is about 1 nanometer-Yue 1000 nanometer, is preferably about 10 nanometer-Yue 500 nanometers, is more preferably about 50 nanometer-Yue 250 nanometers.
In one embodiment, in described device, the thickness of described photoactive layer is about 1 nanometer-Yue 1000 nanometer, is preferably about 10 nanometer-Yue 500 nanometers, is more preferably about 50 nanometer-Yue 250 nanometers.
In one embodiment, in device of the present invention, described photoactive layer is film of the present invention.
In one embodiment, in described device, described anode comprises one or more layers film, and it is gold, silver, fluorine tin oxide, or the film of tin indium oxide; Be preferably the film of tin indium oxide.
In one embodiment, in described device, described negative electrode comprises one or more layers film, and it is barium, calcium, magnesium, indium, aluminium, ytterbium, silver, calcium silver alloys, Al-Li alloy, magnesium silver alloys, or film of its combination; Be preferably the film of Ca/Al.
In one embodiment, device of the present invention is organic photovoltaic battery (OPVs), is preferably body heterojunction organic photovoltaic battery (BHJ OPVs).
As previously mentioned, the OPVs of body heterojunction class, its p-type electron donor material and N-shaped electron acceptor material blended in the photoactive layer of this battery.Therefore, in device of the present invention, described photoactive layer comprises electron acceptor material further.The electron acceptor material be suitable for comprises the common electron acceptor material in this area.Such as, fullerene derivate, such as [6,6]-phenyl-C 61methyl-butyrate (PC 61bM, CAS:160848-22-6), [6,6]-phenyl-C 71methyl-butyrate (PC 71bM, CAS:609771-63-3), [6,6]-phenyl-C 85methyl-butyrate ([84] PCBM, CAS:905843-95-0), [6,6]-phenyl-C 61butyl butyrate (PCBB, CAS:571177-66-7), indenes-C 60two adductss (ICBA, CAS:1207461-57-1); Be preferably PC 61bM or PC 71bM.
In one embodiment, in described device, described photoactive layer comprises electron acceptor material further, described electron acceptor material is preferably selected from [6,6]-phenyl-C 61methyl-butyrate, [6,6]-phenyl-C 71methyl-butyrate, [6,6]-phenyl-C 85methyl-butyrate, [6,6]-phenyl-C 61butyl butyrate, indenes-C 60two adductss; Be preferably PC 61bM or PC 71bM.
In body heterojunction OPVs, its electron donor material and electron acceptor material are normally first dissolved in suitable organic solvent by the preparation method of its photoactive layer, are mixed with and have suitably to the mixing solutions of body/acceptor ratio (D/A ratio); And described mixing solutions is adopted spin coating, brush, spraying, dip-coating, roller coat, silk screen printing, printing or spray ink Printing mode form photoactive layer on negative electrode.Generally speaking, the thickness of photoactive layer controls by the concentration and coating processes condition (rotating speed of such as spin coating) applying the mixing solutions of electron donor material and electron acceptor material.In preparation process, the thickness of described photoactive layer can be surveyed by surface profiler (profilometer) and learn.
In one embodiment, in device of the present invention, the D/A of described photoactive layer is about 1:10 than for about 2:1-, is preferably about 1:1-and is about 1:5.
In addition, in order to increase the energy conversion efficiency (PCE) of described device, device of the present invention also can arrange hole injection layer (hole injection layer, HIL) between described photoactive layer and anode.The preparation of device of the present invention can be used in typical substrate, as glass or flexible substrate, as coated anode on PET polyester; Apply optional hole injection layer more thereon and comprise the photoactive layer of polymkeric substance of formula 1a or 1b; The last negative electrode covering one or more layers in the mode of vacuum evaporation.Those skilled in the art can select suitable negative electrode as the case may be, anode and hole injection layer material and coating processes.
In one embodiment, described device comprises the hole injection layer be arranged between photoactive layer and anode further.
In one embodiment, in described device, described hole injection layer comprises the mixture of poly-(3,4-ethene-dioxythiophene) (PEDOT) and poly-(styrene sulfonate) (PSS).
In one embodiment, device of the present invention sequentially comprises anode // photoactive layer // negative electrode.In another embodiment, device of the present invention sequentially comprises anode // hole injection layer // photoactive layer // negative electrode.
Embodiment
The present invention will illustrate with the following Examples in further detail.Intermediate product (A)-(I), (3A) and final polymer product PT4NIsoI, the detailed synthesis path of PT4NBTD, PT4NTPD lists in embodiment 1-3.Product synthesized in this embodiment is all used 1hNMR characterizes.
Material and sign:
All reagent and raw material be all from can business buy product, use without the need to being further purified, except as otherwise noted.1,5-dihydroxy naphthlene, acid chloride (II), 6-bromo-isatin, 1-octylame, purchased from ladder west, bromo-2,1, the 3-diazosulfides of 4,7-bis-like that (Shanghai) changes into industrial development company limited.Para-methylbenzenepyridinsulfonate sulfonate, 3,4-dihydro-2H-pyrans, pyridine, heptane, trifluoromethanesulfanhydride anhydride, the bromo-decyl of 2-hexyl-1-, tetrahydrofuran (THF), tetrakis triphenylphosphine palladium, 2-bromothiophene is purchased from Sigma-Aldrich company.Connection pinacol borate, three (guaiacyl) phosphine, 1,1 '-bis-(diphenylphosphine) ferrocene Palladous chloride, 6-bromine oxindole is purchased from Shanghai Da Rui fine chemicals company limited.Isosorbide-5-Nitrae-dioxane, [Ir (OCH 3) (C 8h 12)] 2purchased from AlfaAesar.3,4-thiophene dicarboxylic acid is purchased from Frontier Scientific company.Methylene dichloride, sodium bicarbonate, anhydrous magnesium sulfate, acetone, hydrochloric acid, methyl alcohol, toluene, sodium carbonate, sodium-chlor, sherwood oil, dimethyl formamide, ethyl acetate, salt of wormwood, chloroform, N,N-DIMETHYLACETAMIDE, N-bromine succinimide is purchased from traditional Chinese medicines group.
1h NMR (Nuclear Magnetic Resonance) spectrum uses Bruker400MHz Advance II apparatus measures, with the deuterochloroform (CDCl of dilution at 293K 3) or deuterated dimethyl sulfoxide (DMSO-d 6) as solvent.The report of chemical shift is the ppm that benchmark moves down (downfiled) with tetramethylsilane (TMS) displacement, and " s " means unimodal, and " d " means bimodal, " dd " means doublet of doublet, " t " means three peaks, and " q " is four peaks, and " m " means multimodal.
Ultimate analysis uses Organic Element Analysis Instrument Vario EL III apparatus measures.The test of molecular weight uses size-exclusion chromatography (SEC), with tetrahydrofuran (THF) as solvent, then according to polystyrene standard working curve, calculates and obtain the molecular weight of tested polymkeric substance.
Ultraviolet-visible (UV-Vis) absorption spectrum uses Perkin-Elmer Lamba960 Spectrophotometric.
embodiment 1
poly-{ (E)-6-(5-(two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) naphthalene-2-base of 4,8-) thiophene-2-base)-1,1 '-bis-(2-hexyl decyl)-[3,3 '-bis-(indolylidene)]-2,2 '-diketone } the preparation of [PT4NIsoI]
the preparation of two (tetrahydrochysene-2H-pyrans-2-base oxygen base) naphthalene (product A) of steps A: 1,5-
By 1,5-dihydroxy naphthlene (6.40 grams, 39.96 mmoles), the CH of para-methylbenzenepyridinsulfonate sulfonate (2.01 grams, 7.99 mmoles) and 20 milliliters 2cl 2add the reaction flask of 250 milliliters that are placed in ice bath and stir.3,4-dihydro-2H-pyrans (14.58 milliliters, 159.83 mmoles) is dropwise injected via syringe.After 20 minutes, remove ice bath, make reaction mixture be warming up to room temperature and Keep agitation 4 hours.The reaction mixture saturated sodium bicarbonate aqueous solution washing obtained also uses dichloromethane extraction subsequently.Organic extraction after gained merges uses distilled water and salt water washing in succession, and uses anhydrous magnesium sulfate to remove trace water.After filtration, reaction mixture under reduced pressure concentrates.Pass through recrystallization in acetone again and obtain product A (9.68 grams).
1H NMR(CDCl 3,400MHz):δ7.95(d,2H),7.41(dd,2H),7.19(d,2H),5.67(s,2H),4.00(m,2H),3.67(m,2H),2.19(m,2H),1.99-2.10(m,4H),1.76-1.82(m,4H),1.66-1.70(m,2H)。
step B:2,2 '-(two ((tetrahydrochysene-2H-pyrans-2-base) oxygen base) naphthalene-2,6-bis-base of 4,8-) two (4,4,5,5- tetramethyl--1,3,2-dioxaborolanes) preparation of (product B)
By two for 1,5-prepared by abovementioned steps A (tetrahydrochysene-2H-pyrans-2-base oxygen base) naphthalene (1.64 grams, 4.99 mmoles), connection pinacol borate (1.90 grams, 7.49 mmoles), catalyzer [Ir (OCH 3) (C 8h 12)] 2(49.65 milligrams, 74.91 micromoles), and 4,4 '-di-t-butyl-2,2 '-dipyridyl (40.21 milligrams, 149.82 micromoles) is added to the flask of 50 milliliters.By three circulating degasifications of mixture through being undertaken by vacuum and nitrogen purging.10 milliliters are added through degassed heptane via syringe.Reaction mixture remains on 75 DEG C of stirrings and spends the night in nitrogen.The solid of generation is dissolved in 10 milliliters of heptane and by being mounted with silica gel, the post of diatomite and gac.Under reduced pressure concentrated acquisition product B (2.25 grams).
1H NMR(CDCl 3,400MHz):δ8.43(d,2H),7.48(d,2H),5.80(s,2H),4.00(m,2H),3.69(m,2H),1.29-2.23(m,36H)。
step C:2,2 '-((3,7-bis-(thiophene-2-base) naphthalene-1,5-bis-base) two (oxygen base)) two (tetrahydrochysene-2H-pyrrole mutter) preparation of (product C)
By 2 prepared by abovementioned steps B, 2 '-(4, two ((tetrahydrochysene-2H-pyrans-2-base) oxygen base) naphthalene-2 of 8-, 6-bis-base) two (4,4,5,5-tetramethyl--1,3,2-dioxaborolanes) (1.20 grams, 2.07 mmoles) and tetrakis triphenylphosphine palladium (0) (Pd (PPh 3) 4, CAS 14221-01-3) and (119.47 milligrams, 103.39 micromoles) add the reaction flask of 50 milliliters, and with nitrogen purging three times.The flask bubbling 20 minutes of the 2-bromothiophene (809.10 milligrams, 4.96 mmoles) be dissolved in 15 milliliters of toluene will be housed, and be transferred to reaction flask via syringe subsequently.Via the Na of syringe by 1M 2cO 3the aqueous solution (12.41 milliliters) is injected in this reaction flask.Gained yellow solution spends the night 100 DEG C of stirrings, and uses dichloromethane extraction subsequently three times.Gained organic phase is washed in distilled water and salt solution, and subsequently with anhydrous magnesium sulfate drying.After filtration, under reduced pressure solvent is removed, and pass through recrystallization acquisition product C (0.62 gram) in acetone.
1H NMR(CDCl 3,400MHz):δ8.14(d,2H),7.46(m,4H),7.32(m,2H),7.14(d,2H),5.77(s,2H),4.00(m,2H),3.70(d,2H),1.28-2.24(m,6H)。
the system of two (triflate) (product D) of step D:3,7-bis-(thiophene-2-base) naphthalene-1,5-bis-base standby
By 2 prepared by abovementioned steps C, 2 '-((3,7-bis-(thiophene-2-base) naphthalene-1,5-bis-base) two (oxygen base)) two (tetrahydrochysene-2H-pyrans) (1.20 grams, 2.07 mmole), the methylene dichloride of 15 milliliters, and the 1M methanol hydrochloride solution of 12 milliliters to add in flask and to purge with in nitrogen.In the reaction process of this hydroxyl deprotection, solution colour turns to black by yellow.After reaction, under reduced pressure solvent is removed, gained yellow solid is transferred to reaction flask and is dissolved in the methylene dichloride of 20 milliliters.Under nitrogen purge, pyridine (0.25 milliliter) and trifluoromethanesulfanhydride anhydride (0.38 milliliter) is in succession injected via syringe.Reaction mixture is at room temperature stirred 1 hour.The washing of gained mixture saturated sodium bicarbonate aqueous solution also uses dichloromethane extraction subsequently.The organic extraction merged uses water and salt water washing in succession, also under reduced pressure concentrates with anhydrous magnesium sulfate drying.Product D (0.37 gram) is obtained by recrystallization in methylene dichloride.
1H NMR(CDCl 3,400MHz):δ8.23(d,2H),7.86(d,2H),7.52(d,2H),7.46(d,2H),7.20(d,2H)。
step e: 1,1 '-(5,5 '-(3,7-bis-(thiophene-2-base) naphthalene-1,5-bis-base) two (thiophene-5,2-bis-base)) is two the preparation of (2-hexyl-1-in last of the ten Heavenly stems ketone) (product E)
By 3 prepared by abovementioned steps D, 7-bis-(thiophene-2-base) naphthalene-1, two (triflate) (0.30 gram of 5-bis-base, 0.510 mmole), tetrakis triphenylphosphine palladium (0) (0.0295 milligram, 0.0255 micromole) adds three circular treatment also using vacuum and nitrogen purging in the reaction flask of 50 milliliters subsequently.To the 2-hexyl-1-(5-(4 be dissolved in 15 milliliters of toluene be housed, 4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) thiophene-2-base)-1-ketone in the last of the ten Heavenly stems (548.69 milligrams, 1.22 mmoles) flask bubbling 20 minutes and be transferred to reaction flask via syringe subsequently.The Na of 1M is injected via syringe 2cO 3the aqueous solution (5.10 milliliters).Gained solution spends the night 100 DEG C of stirrings.Product extracts three times in methylene dichloride.The organic liquor water merged and salt water washing, with anhydrous magnesium sulfate drying.After filtration, solution under reduced pressure concentrates.Raw product purifies to provide product E by mixed solvent (volumetric ratio is 3:1) the eluting silica gel post with sherwood oil/methylene dichloride, and it is yellow solid (0.28 gram).
1H NMR(CDCl 3,400MHz):δ8.44(d,2H),7.94(d,2H),7.87(d,2H),7.28-7.44(m,6H),7.15(m,2H),3.31(m,2H),1.88(m,8H),1.25-1.58(m,40H),0.87-0.92(m,12H)。
step F: 1,1 '-(5,5 '-(two (5-bromothiophene-2-base) naphthalene-1,5-bis-base of 3,7-) two (thiophene-5,2-bis-base)) the preparation of two (2-hexyl-1-in last of the ten Heavenly stems ketone) (product F)
To 1 prepared by abovementioned steps E, 1 '-(5,5 '-(3,7-bis-(thiophene-2-base) naphthalene-1,5-bis-base) two (thiophene-5,2-bis-base)) two (2-hexyl-1-in last of the ten Heavenly stems ketone) (0.2 gram, 214.25 micromoles) be placed in the reaction flask of 50 milliliters that are equipped with nitrogen inlet and nitrogen bubbler in solution in the dimethyl formamide of 10 milliliters, add N-bromine succinimide (87.71 milligrams, 492.78 micromoles).Allow reaction mixture at room temperature stir spend the night.Gained suspension is poured onto in 100 ml distilled waters be in separating funnel, and extracts three times in ethyl acetate.The organics washed with brine merged, with anhydrous magnesium sulfate drying.After filtration, solution under reduced pressure concentrates.Raw product purifies to provide yellow solid by mixed solvent (volumetric ratio is 3:1) the eluting silica gel post with sherwood oil/methylene dichloride.Obtain product F by precipitation from methyl alcohol, be yellow powder (0.16 gram).
1H NMR(CDCl 3,400MHz):δ8.31(d,2H),7.87(d,2H),7.81(d,2H),7.35(d,2H),7.15(d,2H),7.06(d,2H),3.30(m,2H),0.87-1.87(m,48),0.87-0.92(m,12H)。
step G:6, the preparation of 6 '-dibromo isoindigo (product G)
6,6 '-dibromo isoindigo (product G), 6,6'-bis-bromo-N, N'-(2-hexyl decyl) isoindigo (product H) and 6,6'-dioxaborolanes-N, the synthesis of N'-(2-hexyl decyl) isoindigo (product I) is see R.Stalder etc., Macromolecules2011,44,6303.
In the acetic acid suspension of 50 milliliters, 2 milliliters of concentrated hydrochloric acids are added and reflux 4.5 hours to 6-bromine oxindole (4.24 grams, 20 mmoles) and 6-bromo-isatin (4.52 grams, 20 mmoles).Question response mixture cools, and filters; Gained solids with methanol washs.After vacuum-drying, obtain wine-colored product G (7.05 grams), namely 6,6 '-dibromo isoindigo, directly can be used in next reaction.
the preparation of step H:6,6'-bis-bromo-N, N'-(2-hexyl decyl) isoindigo (product H)
To 6 prepared by abovementioned steps G, 6 '-dibromo isoindigo (2.10 grams, 5 mmoles) and (2.76 grams, salt of wormwood, 20 mmoles) in the dimethylformamide suspension of 20 milliliters, the bromo-decyl of 2-hexyl-1-(3.66 grams, 12 mmoles) is injected via syringe.Reaction mixture is at 100 DEG C, and stirring is spent the night.To be cooled, be then poured into water.Use dichloromethane extraction product wherein, with water and salt water washing organic extract, with anhydrous magnesium sulfate drying, filter.After under reduced pressure being removed by solvent, raw product is dissolved in a small amount of methylene dichloride, precipitates in cold methanol.Raw product purifies to provide product H by mixed solvent (volumetric ratio is 5:1) the eluting silica gel post with sherwood oil/methylene dichloride, 6,6'-bis-bromo-N, N'-(2-hexyl decyl) isoindigo, it is dark red solid (1.5 grams).
1H NMR(CDCl 3,400MHz):δ9.06(d,2H),7.15(m,2H),6.90(d,2H),3.60(m,4H),1.89(m,2H),1.28-1.40(m,48H),0.87-0.92(m,12H)。
the preparation of step I:6,6'-dioxaborolanes-N, N'-(2-hexyl decyl) isoindigo (product I)
By 6 prepared by abovementioned steps H, 6'-bis-bromo-N, N'-(2-hexyl decyl) isoindigo (900 milligrams, 1.04 mmoles), connection pinacol borate (631.3 milligrams, 2.49 mmoles), 1,1 '-bis-(diphenylphosphine) ferrocene Palladous chloride (25.38 milligrams, 0.031 mmole), Potassium ethanoate (304.96 milligrams, 3.11 mmoles) adds the reaction flask of 50 milliliters, and with nitrogen purging three times.Isosorbide-5-Nitrae-the dioxane (10 milliliters) of degassed drying is injected in reaction flask by syringe.Mixed solution is being heated to 80 DEG C, stirs under nitrogen protection and spends the night.To be cooled, be then poured into water.Use dichloromethane extraction product wherein, with water and salt water washing, with anhydrous magnesium sulfate drying.After under reduced pressure being removed by solvent, raw product is dissolved in a small amount of methylene dichloride, precipitates in methyl alcohol.Raw product purifies to provide product I by mixed solvent (volumetric ratio is 2:1) the eluting silica gel post with sherwood oil/methylene dichloride, 6,6'-dioxaborolanes-N, N'-(2-hexyl decyl) isoindigo, it is black solid (0.47 gram).
1H NMR(CDCl 3,400MHz):δ9.15(d,2H),7.48(d,2H),7.18(d,2H),3.70(m,4H),1.95(m,2H),0.86-1.46(m,84H)。
step J: poly-{ (E)-6-(5-(two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) of 4,8- naphthalene-2-base) thiophene-2-base)-1,1 '-bis-(2-hexyl decyl)-[3,3 '-bis-(indolylidene)]-2,2 '- diketone } preparation of [PT4NIsoI]
By 1 prepared by abovementioned steps F, 1 '-(5, 5 '-(3, two (5-bromothiophene-2-base) naphthalene-1 of 7-, 5-bis-base) two (thiophene-5, 2-bis-base)) two (2-hexyl-1-in last of the ten Heavenly stems ketone) (200 milligrams, 0.183 mmole), prepared by step I 6, 6'-dioxaborolanes-N, N'-(2-hexyl decyl) isoindigo (176.5 milligrams, 0.183 mmole), three (dibenzalacetone) two palladium (0) (13.4 milligrams, 14.7 micromole), (119.4 milligrams, salt of wormwood, 0.367 mmole) and three (guaiacyl) phosphine (10.34 milligrams, 0.0294 mmole) add in the microwave reactor of 10 milliliters and seal.Then mixture is vacuumized/inflated with nitrogen, circulate three times.The tetrahydrofuran (THF) (4 milliliters) of degassed drying is expelled in microwave reactor.Mixture is heated to 90 DEG C under microwave radiation, continues 120 minutes.After question response completes, mixture is poured in methyl alcohol, by collected by vacuum filtration precipitate.This polymkeric substance is extracted by soxhlet extraction, first uses acetone and sherwood oil to wash away impurity, then uses chloroform extraction product.Chloroformic solution is concentrated to and is less than 10 milliliters, then will be settled out product with methyl alcohol.Obtain formula 1a polymer product by filtered and recycled, PT4NIsoI, it is dark green solid (0.18 gram).
1H NMR(CDCl 3,400MHz):δ9.23(br,2H),9.00(br,2H),8.50(br,2H),7.92(br,2H),7.45(br,2H),7.04(br,8H),3.31-3.76(m,8H),0.21-1.92(m,120H)。
Number-average molecular weight (the M of formula 1a polymer P T4NIsoI n) and weight-average molecular weight (M w) be respectively 15.8kDa and 37.7kDa, its molecular weight dispersion index (PDI, i.e. M w/ M nvalue) be 2.38.Estimate according to its number-average molecular weight, the m value of PT4NIsoI is 10.
embodiment 2
poly-{ 1,1'-(5,5'-(3-(5-(benzo [c] [1,2,5] thiadiazoles-4-base) thiophene-2-base)-7-(thiophene-2-base) naphthalene-1,5-bis-base) two (thiophene-5,2-bis-base)) two (2-hexyl-1-in last of the ten Heavenly stems ketone) } preparation of [PT4NBTD]
By 1 prepared by the step e of embodiment 1,1 '-(5,5 '-(3,7-bis-(thiophene-2-base) naphthalene-1,5-bis-base) two (thiophene-5,2-bis-base)) two (2-hexyl-1-in last of the ten Heavenly stems ketone) (171 milligrams, 0.183 mmole), 4,7-bis-bromo-2,1,3-diazosulfide (63.0 milligrams, 0.183 mmole), (44.4 milligrams, salt of wormwood, 0.321 mmole), acid chloride (II) (1.9 milligrams, 0.009 mmole) adds in the microwave reactor of 10 milliliters and seals.Then mixture is vacuumized/inflated with nitrogen, circulate three times.The N,N-DIMETHYLACETAMIDE (DMAc) (2 milliliters) of degassed drying is expelled in microwave reactor.Mixture is heated to 110 DEG C under microwave radiation, continues 180 minutes.After question response completes, mixture is poured in methyl alcohol, by collected by vacuum filtration precipitate.This polymkeric substance is extracted by soxhlet extraction, first uses acetone and sherwood oil to wash away impurity, then uses chloroform extraction product.Chloroformic solution is concentrated to and is less than 10 milliliters, then will be settled out product with methyl alcohol.Obtain formula 1a polymer product by filtered and recycled, PT4NBTD, it is black solid (95 milligrams).
1H NMR(DMSO-d 6,400MHz):δ8.32(br,2H),7.24(br,4H),6.67(br,4H),5.34(br,4H),0.84-2.67(m,60H)。
The M of formula 1a polymer P T4NBTD nand M wbe respectively 9.1kDa and 36.9kDa, its PDI is 4.06.Estimate according to its number-average molecular weight, the m value of PT4NBTD is 10.
embodiment 3
poly-{ 1-(5-(two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) naphthalene-2-base of 4,8-) thiophene fen-2-base)-5-octyl group-4H-thieno-[3,4-c] pyrroles-4,6 (5H)-diketone } system of [PT4NTPD] standby
steps A: the preparation of 5-octyl group-4H-thieno-[3,4-c] pyrroles-4,6 (5H)-diketone (product 3A)
The preparation of 5-octyl group-4H-thieno-[3,4-c] pyrroles-4,6 (5H)-diketone see P.Berrouard etc., J.Org.Chem.2012,77,8167.By 3,4-thiophene dicarboxylic acid (1.00 grams, 5.81 mmoles), 1-octylame (0.7 gram, 5,81 mmoles) joins in microwave reactor and seals.Mixture is heated to 240 DEG C under microwave radiation, continues 10 minutes.After question response completes, product is dissolved in methylene dichloride, and by having the eluting silica gel post that methylene dichloride is solvent.Product washing with acetone after concentrated is to obtain 5-octyl group-4H-thieno-[3, the 4-c] pyrroles-4,6 (5H)-diketone (0.62 gram) that product 3A is white solid.
1HNMR(CDCl 3,400MHz):δ7.83(s,2H),3.63(t,2H),1.66(s,2H),1.31(t,10H),0.89(t,3H)。
step B: poly-{ 1-(5-(two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) naphthalene-2-of 4,8- base) thiophene-2-base)-5-octyl group-4H-thieno-[3,4-c] pyrroles-4,6 (5H)-diketone } [PT4NTPD] preparation
To prepare according to the step F of embodiment 11, 1 '-(5, 5 '-(3, two (5-bromothiophene-2-base) naphthalene-1 of 7-, 5-bis-base) two (thiophene-5, 2-bis-base)) two (2-hexyl-1-in last of the ten Heavenly stems ketone) (200 milligrams, 0.183 mmole), according to the 5-octyl group-4H-thieno-[3 in the present embodiment prepared by steps A, 4-c] pyrroles-4, 6 (5H)-diketone (48.6 milligrams, 0.183 mmole), (89.9 milligrams, salt of wormwood, 0.916 mmole), acid chloride (II) (1.7 milligrams, 7.3 micromoles) add in the microwave reactor of 10 milliliters and seal.Then mixture is vacuumized/inflated with nitrogen, circulate three times.The tetrahydrofuran (THF) (2 milliliters) of degassed drying is expelled in microwave reactor.Mixture is heated to 90 DEG C under microwave radiation, continues 120 minutes.After question response completes, mixture is poured in methyl alcohol, by collected by vacuum filtration precipitate.This polymkeric substance extracts through soxhlet extraction, first uses acetone and sherwood oil to wash away impurity, then uses chloroform extraction product.Chloroformic solution is concentrated to and is less than 10 milliliters, then will be settled out product with methyl alcohol.Obtain formula 1a polymer product by filtered and recycled, PT4NTPD, it is dark red solid (0.12 gram).
1HNMR(CDCl 3,400MHz):δ8.32(d,2H),7.88(d,2H),7.83(d,2H),7.38(d,2H),7.18(d,2H),7.10(d,2H),3.66(m,2H),3.29(m,2H),1.28-1.88(m,60H),0.87-0.90(m,15H)。
The M of formula 1a polymer P T4NTPD nand M wbe respectively 61.5kDa and 124kDa, its PDI is 2.03.Estimate according to its number-average molecular weight, the m value of PT4NTPD is 50.
embodiment 4
the optical property of formula 1a polymkeric substance
The polymkeric substance (10 milligrams) of the formula 1a prepared by embodiment 1-3 is dissolved in spectrum level chloroform, the solution being mixed with 2 mg/ml puts quartz sample pool (1cmx1cm), be spectrum level chloroform in reference cell, use its uv-visible absorption spectra in chloroformic solution of Perkin-ElmerLamba960 spectrophotometer measurement.By the sample solution of described preparation, use sol evenning machine with the rotating speed spin coating 60 seconds of 1500rpm in glass substrate, rear formation sample dry film to be dried, then measure its uv-visible absorption spectra when solid-state.
As shown in figure 1 and table 1, the formula 1a polymkeric substance prepared by embodiment 1, the major absorbance peak (λ of PT4NIsoI in chloroformic solution max) at 603nm place, and major absorbance peak when it is solid-state is at 612nm place.The absorption peak of PT4NIsoI when solid-state originates in 744nm (λ onset), estimate its optical band gap (Eg opt) be 1.67 electron-volts.
As shown in Figure 2 and Table 1, the major absorbance peak of the formula 1a polymer P T4NBTD prepared by embodiment 2 in chloroformic solution is at 512nm place, and major absorbance peak when it is solid-state is at 515nm place.The absorption peak of PT4NBTD when solid-state originates in 701nm, estimates that its optical band gap is 1.77 electron-volts.
As shown in Figure 3 and Table 1, the major absorbance peak of the formula 1a polymer P T4NTPD prepared by embodiment 3 in chloroformic solution is at 478nm place, and its solid-state major absorbance peak is at 518nm place.The absorption peak of PT4NTPD when solid-state originates in 596nm, estimates that its optical band gap is 2.08 electron-volts.
table 1
Known to electron donor material, it is preferred that its absorption peak originates in 700-800nm scope, represents that this donor material has higher light collecting light ability in low frequency range.So can be better than PT4NTPD as electron donor material PT4NIsoI and PT4NBTD.
Similarly, compare their optical band gap value, PT4NIsoI and PT4NBTD can absorb the lower photon of more multi-energy than PT4NTPD.
the characterization device of photovoltaic device
The manufacturing step of all photovoltaic devices and sign are measured and are implemented all in a nitrogen atmosphere or in glove box.The area of obtained photovoltaic device is 4mm 2.Use the thickness of each layer in the VeecoDektak150 surface profiler measuring element structure of accuracy ± 1 nanometer.Use AM1.5G solar simulator (SANEIXES-70S1) at 100mW/cm 2under light intensity, measure the performance of obtained photovoltaic device.The light intensity of this solar simulator is calibrated with standard P V reference cell: i.e. 3.980cm 2monocrystaline silicon solar cell, and standard P V reference cell used is at NREL, Milpitas, CA, USA were calibrated.Use Keithley2400 record current density vs. voltage (J-V) curve.
The photovoltaic performance of organic photovoltaic devices is normally assessed with several important parameters, comprises open circuit voltage (V oc), short-circuit current density (J sc), packing factor (fillfactor, FF) and energy conversion efficiency (PCE).Their specific definition is well known to those skilled in the art, and see the work such as " semi-conductor and metallicity polymkeric substance " A.J.Heeger, handsome will is firm etc. translates, and Science Press, publishes for 2010, the 13rd chapter.
embodiment 5
the manufacture of the photovoltaic device of contained 1a polymer P T4NIsoI
Use PT4NIsoI prepared by embodiment 1 as electron donor(ED), PC 71bM as electron acceptor(EA), and is sequentially ITO//PEDOT:PSS//PT4NIsoI:PC with the structure of anode // hole injection layer // photoactive layer // negative electrode 71bM//Ca/Al manufactures photovoltaic device.
Glass ITO through ultrasonic clean being applied (thick about 150 nanometers) is used as transparent anode.ITO surface by be exposed to UV ozone spin coating PEDOT:PSS after 25 minutes ( pVPAI4083, purchased from H.C.Starck company) film be used as hole injection layer.This layer in an oven in 150 DEG C dry 10 minutes in atmosphere.By PT4NIsoI and PC 71bM (purchased from AlfaAesar) miscellany is as photoactive layer, and be respectively 1:2 to body and acceptor ratio (i.e. D/A ratio), the part by weight of 1:3 or 1:4 is dissolved in chloroform.Be that the blend solution of 10 mg/ml is spun on the PEDOT:PSS film of dry thick 30 nanometers by total concn.The form (morphology) of described photoactive layer adjusts by controlling solvent seasoning condition.The spin coating speed adopted is 3500rpm, and rotational time is 40 seconds.The device work in-process of good for spin coating photoactive layer are dry, obtain the photoactive layer of thick about 90 nanometers.Finally, by being less than 1 × 10 -5ca (about 18 nanometer) is deposited under the vacuum of holder, then depositing Al (about 80 nanometer), be namely used as negative electrode with Ca/Al, thus obtained organic photovoltaic devices sample 5A, 5B and 5C.
The photovoltaic device of embodiment 5A-5C is BHJ type device, and its photoactive layer contains formula 1a polymer P T4NIsoI and PC 71bM, and its D/A ratio is respectively 1:2,1:3 and 1:4; Its relevant solar cell parameter and J-V figure, see table 2 and Fig. 4.Comprise in the photovoltaic device of PT4NIsoI by observing in the J-V curve of Fig. 4 at three, the packing factor (FF) of sample 5B is maximum (57.42%), and its effciency of energy transfer (PCE) is also the highest (0.50%).
table 2
embodiment 6
the manufacture of the photovoltaic device of contained 1a polymer P T4NBTD
Use PT4NBTD prepared by embodiment 2 as electron donor(ED), PC 71bM as electron acceptor(EA), and is sequentially ITO//PEDOT:PSS//PT4NBTD:PC with the structure of anode // hole injection layer // photoactive layer // negative electrode 71bM//Ca/Al manufactures photovoltaic device.
Glass ITO through ultrasonic clean being applied (thick about 150 nanometers) is used as transparent anode.ITO surface by be exposed to UV ozone after 25 minutes spin coating PEDOT:PSS film be used as hole injection layer.This layer in an oven in 150 DEG C dry 10 minutes in atmosphere.By PT4NBTD and PC 71bM miscellany as photoactive layer, and is dissolved in orthodichlorobenzene (ODCB, purchased from Acros Organics) with D/A than for the part by weight of 1:1.Be that the blend solution of 20 mg/ml is spun on dry PEDOT:PSS film (thick about 30 nanometers) by total concn.The spin coating speed adopted is 700rpm, and rotational time is 40 seconds.By the device work in-process of good for spin coating photoactive layer convection drying under room temperature in glove box, obtain the photoactive layer of about 100 nanometer thickness, resulting devices obtained thus is then marked as without thermal annealing sample A.On the hot-plate another device work in-process through same process being placed in 100 DEG C dry 10 minutes, namely through " thermal annealing " process, resulting devices obtained thus was then marked as through thermal annealing sample B.Finally, by being less than 1 × 10 -5ca (about 18 nanometer) is deposited under the vacuum of holder, then depositing Al (about 80 nanometer), be namely used as negative electrode with Ca/Al, thus obtained organic photovoltaic devices sample 6A and 6B.
The photovoltaic device of embodiment 6A-6B is BHJ type device, and its photoactive layer contains formula 1a polymer P T4NBTD and PC 71bM, its D/A are than being 1:1; Its relevant solar cell parameter and J-V figure, see table 3 and Fig. 5.Can be observed the sample 6B through thermal annealing by the data of table 3, compared to the sample 6A without thermal annealing, there is higher open circuit voltage (V oc, 0.81V) and have energy conversion efficiency (PCE) (0.70%) that significantly improves.
table 3
embodiment 7
the manufacture of the photovoltaic device of contained 1a polymer P T4NTPD
Use PT4NTPD prepared by embodiment 1 as electron donor(ED), PC 61bM as electron acceptor(EA), and is sequentially ITO//PEDOT:PSS//PT4NTPD:PC with the structure of anode // hole injection layer // photoactive layer // negative electrode 61bM//Ca/Al manufactures photovoltaic device.
Glass ITO through ultrasonic clean being applied (thick about 150 nanometers) is used as transparent anode.ITO surface by be exposed to UV ozone after 25 minutes spin coating PEDOT:PSS film be used as hole injection layer.This layer in an oven in 150 DEG C dry 10 minutes in atmosphere.By PT4NTPD and PC 61bM (purchased from TCI) miscellany as photoactive layer, and is dissolved in chloroform with D/A than the part by weight being respectively 1:1 or 1:2.Be that the blend solution of 24 mg/ml is spun on the PEDOT:PSS film of dry thick about 30 nanometers by total concn.The spin coating speed adopted is 2000rpm, and rotational time is 40 seconds.The drying of the device work in-process of spun photoactive layer is obtained the photoactive layer of thick about 90 nanometers.By being less than 1 × 10 -5ca (about 18 nanometer) is deposited under the vacuum of holder, then depositing Al (about 80 nanometer), be namely used as negative electrode with Ca/Al, thus obtained organic photovoltaic devices sample 7A and 7B.
The photovoltaic device of embodiment 7A-7B is BHJ type device, and its photoactive layer contains formula 1a polymer P T4NTPD and PC 61bM, its D/A ratio is respectively 1:1 and 1:2; Its relevant solar cell parameter and J-V figure, see table 4 and Fig. 6.Slightly better than sample 7A by the every solar cell parameter that can be observed sample 7B in table 4; Its short-circuit current (J sc) be 0.93mA/cm -2and its effciency of energy transfer is 0.19%.
table 4
Although the present invention is illustrated with typical embodiment and describes, and do not mean that it is limited in shown details, because multiple amendment may be there is under spirit of the present invention and substitutes not deviating from.Thus, when those skilled in the art only use normal experiment just can obtain with the improvement of invention disclosed herein and be equal to, and believe that these improve and are equal in the spirit and scope of the present invention defined all in the claims.

Claims (15)

1. the polymkeric substance of formula 1a or 1b:
Wherein
G 1and G 2be selected from vinyl independently of one another, ethynyl, C 6-C 20substituted or unsubstituted arylidene, preferred unsubstituted arylidene, and comprise 1,2 or 3 heteroatomic C independently selected from O, S and N 4-C 12substituted or unsubstituted heteroaryl, preferred unsubstituted heteroaryl; Described heteroatoms is preferably 1 or 2 S atom;
A 1and A 2be selected from independently of one another
D 1and D 2be selected from independently of one another
X is C (O), C (S), C (O) O, or C (S) O, preferred C (O);
Y is C 1-C 30alkyl, preferred C 6-C 24alkyl, also preferred C 10-C 20alkyl; C 2-C 30thiazolinyl, preferred C 6-C 24thiazolinyl, also preferred C 10-C 20thiazolinyl; C 3-C 20cycloalkyl, preferred C 3-C 16cycloalkyl, also preferred C 3-C 12cycloalkyl; C 3-C 20cycloalkenyl group, preferred C 3-C 16cycloalkenyl group, also preferred C 3-C 12cycloalkenyl group; C 4-C 30cycloalkylalkyl, preferred C 4-C 24cycloalkylalkyl, also preferred C 4-C 20cycloalkylalkyl; C 4-C 30cycloalkenyl alkyl, preferred C 4-C 24cycloalkenyl alkyl, also preferred C 4-C 20cycloalkenyl alkyl; C 2-C 20heterocyclic radical, preferred C 2-C 14heterocyclic radical, also preferred C 3-C 10heterocyclic radical; C 3-C 30cycloheteroalkylalkyl, preferred C 3-C 22cycloheteroalkylalkyl, also preferred C 3-C 18cycloheteroalkylalkyl; C 6-C 20aryl, preferred C 6-C 16aryl, also preferred C 6-C 12aryl; Or C 5-C 20heteroaryl, preferred C 5-C 16heteroaryl, also preferred C 5-C 12heteroaryl;
Z is C 1-C 30alkyl, preferred C 6-C 24alkyl, also preferred C 10-C 20alkyl; C 2-C 30thiazolinyl, preferred C 6-C 24thiazolinyl, also preferred C 10-C 20thiazolinyl; C 3-C 20cycloalkyl, preferred C 3-C 16cycloalkyl, also preferred C 3-C 12cycloalkyl; C 3-C 20cycloalkenyl group, preferred C 3-C 16cycloalkenyl group, also preferred C 3-C 12cycloalkenyl group; C 4-C 30cycloalkylalkyl, preferred C 4-C 24cycloalkylalkyl, also preferred C 4-C 20cycloalkylalkyl; C 4-C 30cycloalkenyl alkyl, preferred C 4-C 24cycloalkenyl alkyl, also preferred C 4-C 20cycloalkenyl alkyl; C 2-C 20heterocyclic radical, preferred C 2-C 14heterocyclic radical, also preferred C 3-C 10heterocyclic radical; C 3-C 30cycloheteroalkylalkyl, preferred C 3-C 22cycloheteroalkylalkyl, also preferred C 3-C 18cycloheteroalkylalkyl; C 6-C 20aryl, preferred C 6-C 16aryl, also preferred C 6-C 12aryl; Or C 5-C 20heteroaryl, preferred C 5-C 16heteroaryl, also preferred C 5-C 12heteroaryl;
Q is the integer of 1-3, preferably 1 or 2, also preferably 1;
M is the integer of 5-100, preferred 8-60; With
N is the integer of 5-100, preferred 8-60.
2. the polymkeric substance of claim 1, wherein G 1and G 2be selected from vinyl independently of one another, ethynyl, phenyl, xenyl, naphthyl, binaphthylyl, Azulene base, anthryl, naphthacenyl, base, pyrenyl, thienyl, thiophthene base, and thienothiophene base; Be preferably selected from phenyl, thienyl, thiophthene base and thienothiophene; Also be preferably thienyl.
3. the polymkeric substance of claim 1, wherein
D 1and D 2m-1;
X is C (O);
Y is C 1-C 30alkyl, C 3-C 20cycloalkyl, C 4-C 30cycloalkylalkyl, C 2-C 20heterocyclic radical, or C 3-C 30cycloheteroalkylalkyl; And/or
Q is 1 or 2, is preferably 1.
4. the polymkeric substance of claim 1, wherein
A 1and A 2be identical, and be selected from Ar-1, Ar-3, and Ar-4; With
Z is C 1-C 30alkyl, C 3-C 20cycloalkyl, C 4-C 30cycloalkylalkyl, C 2-C 20heterocyclic radical, or C 3-C 30cycloheteroalkylalkyl.
5. the polymkeric substance of claim 1, it is poly-{ (E)-6-(5-(4, two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) naphthalene-2-base of 8-) thiophene-2-base)-1, 1 '-bis-(2-hexyl decyl)-[3, 3 '-bis-(indolylidene)]-2, 2 '-diketone }, poly-{ 1, 1'-(5, 5'-(3-(5-(benzo [c] [1, 2, 5] thiadiazoles-4-base) thiophene-2-base)-7-(thiophene-2-base) naphthalene-1, 5-bis-base) two (thiophene-5, 2-bis-base)) two (2-hexyl-1-in last of the ten Heavenly stems ketone) }, or poly-{ 1-(5-(4, two (5-(2-hexyl decanoyl) thiophene-2-base)-6-(thiophene-2-base) naphthalene-2-base of 8-) thiophene-2-base)-5-octyl group-4H-thieno-[3, 4-c] pyrroles-4, 6 (5H)-diketone }.
6. film, its polymkeric substance comprising formula 1a according to any one of claim 1-5 or 1b is used as electron donor material, and the thickness of wherein said film is 1 nanometer-1000 nanometer.
7. the film of claim 6, it comprises electron acceptor material further, wherein said electron acceptor material is selected from [6,6]-phenyl-C 61methyl-butyrate, [6,6]-phenyl-C 71methyl-butyrate, [6,6]-phenyl-C 85methyl-butyrate, [6,6]-phenyl-C 61butyl butyrate, indenes-C 60two adductss; Be preferably [6,6]-phenyl-C 61methyl-butyrate or [6,6]-phenyl-C 71methyl-butyrate.
8. comprise anode, the device of negative electrode and photoactive layer, wherein said photoactive layer comprises the polymkeric substance of claim 1, and its thickness is 1 nanometer-1000 nanometer.
9. the device of claim 8, wherein said photoactive layer comprises electron acceptor material further, it is selected from [6,6]-phenyl-C 61methyl-butyrate, [6,6]-phenyl-C 71methyl-butyrate, [6,6]-phenyl-C 85methyl-butyrate, [6,6]-phenyl-C 61butyl butyrate, indenes-C 60two adductss; Be preferably [6,6]-phenyl-C 61methyl-butyrate or [6,6]-phenyl-C 71methyl-butyrate.
10. the device of claim 8, wherein said anode comprises one or more layers film, and it is gold, silver, fluorine tin oxide, or the film of tin indium oxide; Be preferably the film of tin indium oxide.
The device of 11. claims 8, wherein said negative electrode comprises one or more layers film, and it is barium, calcium, magnesium, indium, aluminium, ytterbium, silver, calcium silver alloys, Al-Li alloy, magnesium silver alloys, or film of its combination; Be preferably the film of Ca/Al.
The device of 12. claims 8, comprises the hole injection layer be arranged between photoactive layer and anode further.
The device of 13. claims 12, wherein said hole injection layer comprises the mixture of poly-(3,4-ethene-dioxythiophene) and poly-(styrene sulfonate).
The device of 14. claims 8, described device is body heterojunction organic photovoltaic battery.
Polymkeric substance according to any one of 15. claim 1-5 is used for the purposes of organic photovoltaic battery, and wherein said polymkeric substance is used as electron donor material.
CN201310532879.XA 2013-10-31 2013-10-31 Conjugated polymer based on naphthalene and application thereof Active CN104592491B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310532879.XA CN104592491B (en) 2013-10-31 2013-10-31 Conjugated polymer based on naphthalene and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310532879.XA CN104592491B (en) 2013-10-31 2013-10-31 Conjugated polymer based on naphthalene and application thereof

Publications (2)

Publication Number Publication Date
CN104592491A true CN104592491A (en) 2015-05-06
CN104592491B CN104592491B (en) 2017-03-01

Family

ID=53118577

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310532879.XA Active CN104592491B (en) 2013-10-31 2013-10-31 Conjugated polymer based on naphthalene and application thereof

Country Status (1)

Country Link
CN (1) CN104592491B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130112982A (en) * 2012-04-02 2013-10-15 주식회사 유니플러스 Low band gap polymers, the synthesis of the polymers, and the organic photovoltaic cell

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130112982A (en) * 2012-04-02 2013-10-15 주식회사 유니플러스 Low band gap polymers, the synthesis of the polymers, and the organic photovoltaic cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JON E. CARL´ ET AL: "Polymers for organic photovoltaics based on", 《JOURNAL OF PHOTONICS FOR ENERGY》 *

Also Published As

Publication number Publication date
CN104592491B (en) 2017-03-01

Similar Documents

Publication Publication Date Title
CN103288848B (en) Benzo three thiophenes and its production and use
JP6051206B2 (en) Novel photoactive polymer
CN104744676B (en) Conjugated polymer containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline and application
CN103140492A (en) Semiconductors based on diketopyrrolopyrroles
CN105017264B (en) A kind of organic molecule photoelectric functional material and preparation method thereof
CN107207534A (en) Heterocyclic compound and the organic solar batteries comprising it
JP5425338B2 (en) Copolymer containing anthracene and pearselenol, its production method and its application
CN104744675B (en) Conjugated polymer and its application containing 6H-pyrrolo- [3,4-f] BTA-5,7-diketone
Zhao et al. Isomers of dialkyl diketo-pyrrolo-pyrrole: Electron-deficient units for organic semiconductors
KR20140010156A (en) Semiconducting polymers
CN111533886A (en) Donor-receptor type polymer containing fused ring unit based on quinoxalinebenzotriazole and preparation method and application thereof
KR20200131166A (en) Three component copolymers for semiconductor, Preparation method thereof and Organic semiconductor device comprising the same
CN107805254A (en) A kind of porphyrin small molecule perovskite cathode cushioning layer material and preparation method and application
CN105637009A (en) Copolymer and organic solar cell comprising same
CN109956955B (en) Star-shaped D-A structure conjugated molecule based on benzo-tri (cyclopenta-bi-pentabasic aromatic heterocycle), and preparation method and application thereof
CN109517142B (en) Star-shaped D-A structure conjugated molecule based on tri-indeno five-membered aromatic heterocycle, and preparation method and application thereof
CN103304568B (en) Trimerization Benzazole compounds and its production and use
KR101595919B1 (en) organinc semiconductor compound and organic solar cell having them
CN106700039B (en) Fluorinated pyridine [3,4-b] pyrazine compound and fluorinated pyridine [3,4-b] pyrazinyl copolymer material and application
KR102291239B1 (en) N-type organic semiconducting compounds, manufacturing method thereof, and organic photovoltaics containing the same
CN112390813B (en) Non-fullerene electron acceptor material and organic photovoltaic cell
WO2023179275A1 (en) Fused ring unit based on quinoxaline derivative, small molecule containing same, polymer, preparation methods and use
CN103119046A (en) Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectric applications
KR102114177B1 (en) Novel compound, its production method and organic electronic device using them
CN114349771B (en) Hexabenzocoronene-based non-fullerene acceptor material and preparation and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190823

Address after: 3 buildings and 3 buildings of 588 Wutaishan Road, Suzhou High-tech Zone, Jiangsu Province

Patentee after: Suzhou Tachyon Amperex Technology Limited

Address before: Wilmington, Delaware, USA

Patentee before: E. I. du Pont de Nemours and Co.