Naphthalimide and pyrene alternately condensed fused ring aryl imide derivative and preparation method thereof

Abstract

The invention discloses a naphthalimide and pyrene alternately condensed fused ring aromatic imide derivative as well as a preparation method and application thereof, tetrabromonaphthalene diimide and a heteroatom condensed fused ring aromatic imide derivative are taken as raw materials, under the protection of inert gas, an aromatization reaction is carried out through palladium catalysis, and the naphthalimide and pyrene alternately condensed fused ring aromatic imide derivative is obtained. The fused ring aryl imide derivative alternately fused by naphthalimide and pyrene is prepared by a one-step method. The fused ring aryl imide derivative alternately fused by naphthalimide and pyrene disclosed by the invention has relatively strong absorption on visible light with the wavelength of about 400-700nm, and has relatively high fluorescence quantum yield; the TGA test shows that the thermal decomposition temperature of the derivative is higher than 340 DEG C, which indicates that the derivative has good chemical stability and can be used as an organic semiconductor n-type electron transport material to be applied to organic field effect transistors, solar cell materials, liquid crystal materials, organic light-emitting materials, industrial dyes and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic photoelectric materials, and specifically relates to a condensed-ring aromatic imide derivative formed by alternating fusion of naphthaleneimide and pyrene, and a preparation method and application thereof. Background Art

[0002] Naphthalimide is an important class of organic optoelectronic functional molecules. This is because these compounds have good chemical stability and excellent optoelectronic properties. They have been widely used in organic optoelectronic functional materials, such as solar cell materials, liquid crystal materials, organic field effect transistors, luminescent materials, etc. Due to its excellent optoelectronic properties and broad application prospects, the chemical modification of naphthalimide has received extensive attention from researchers.

[0003] Pyrene is a very good blue chromophore with high fluorescence quantum efficiency and good thermal stability. It is also an excellent electron donor and acceptor material and is widely used in the research of organic light-emitting diodes, organic field-effect transistors, fluorescent probes, organic solar cells, DNA-multichromophore systems, etc. At the same time, pyrene and its derivatives are considered to be one of the preferred building blocks for expanding condensed ring conjugated systems due to their large planar condensed ring structure.

[0004] At present, the research on aromatization methods is mainly based on the influence of factors such as reaction activity between electron-rich and electron-rich systems and between electron-deficient and electron-deficient systems. There is an extreme lack of efficient one-step aromatization methods. Most of them use Suzuki coupling and CH bond transfer, or Stille coupling and CH bond transfer to achieve aromatization. In the process of using Suzuki coupling and CH bond transfer, or Stille coupling and CH bond transfer to achieve aromatization, a large number of single-bond chain by-products will inevitably be produced, resulting in an extremely low aromatization yield. Summary of the invention

[0005] In order to solve the above problems existing in the prior art, the present invention provides a condensed-ring aromatic imide derivative alternately fused with naphthalene imide and pyrene and a preparation method thereof. The condensed-ring aromatic imide derivative alternately fused with naphthalene imide and pyrene is used as a light-absorbing material or an electron transport material in an organic field effect transistor, an organic electroluminescent device, an organic thermochromic element or an organic solar cell.

[0006] The technical solution adopted by the present invention is:

[0007] The present invention provides a condensed-ring aromatic imide derivative in which naphthalene imide and pyrene are alternately fused, and the structure is shown in formula (I) or formula (II):

[0008]

[0009] Where: R 1 are selected from any of the following groups: each independently represents hydrogen, a group containing a substituent or a group without a substituent, and the group is C 1-60 Alkyl, C 1-60 Alkoxy, C 3-60 Cycloalkyl, C 5-60 Aryl, C 1-60 Alkyl aryl, C 1-60 Alkyl heteroaryl, C 1-60 Alkyl heterocyclic group, C 1-60 Alkyleneoxyalkyl, C 1-60 Alkyleneoxyaryl, C 1-60 Alkyleneoxyheteroaryl or C 1-60 Alkyleneoxyheterocyclyl; R 1 Same or different;

[0010] R 2 Any one of the following groups: each independently represents hydrogen, halogen (F, Cl, Br, I), a group containing or not containing a substituent, wherein the group is C 1-60 Alkyl, C 1-60 Alkoxy, C 3-60 Cycloalkyl, C 5-60 Aryl, C 1-60 Alkyl aryl, C 1-60 Alkyl heteroaryl, C 1-60 Alkyl heterocyclic group, C 1-60 Alkyleneoxyalkyl, C 1-60 Alkyleneoxyaryl, C 1-60 Alkyleneoxyheteroaryl, C 1-60 Alkyleneoxy heterocyclic group, cyclopentadienyl, 2,2'-biphenyldiyl, R 2 Same or different;

[0011] The aromatic groups Ar on both sides in formula (II) are selected from any of the following groups: the aromatic groups are selected from phenyl, cyclopentadienyl, cyclopentadienyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, tetraphenyl, pentphenyl, hexaphenyl, pyrenyl, indenyl, fluorenyl or heteroaryl groups which may contain or not contain substituents.

[0012] The condensed-ring aromatic imide derivatives of naphthylimide and pyrene alternately fused can be used as organic semiconductor n-type electron transport materials and applied to organic field effect transistors, organic electroluminescent devices, organic thermochromic elements, organic solar cells and the like.

[0013] The alkyl group is selected from any one or a combination of the following groups: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl or eicosyl, which may or may not contain a substituent.

[0014] The alkoxy group is selected from any one or a combination of the following groups: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanyloxy, octadecyloxy, nonadecanyloxy or eicosyloxy, which may or may not contain a substituent;

[0015] The aryl group is selected from any one or a combination of the following groups: phenyl, cyclopentadienyl, cyclopentadienyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, tetraphenyl, pentacene, hexaphenyl, pyrenyl, indenyl or fluorenyl, which may or may not contain a substituent.

[0016] The heterocyclic group is selected from any one or a combination of the following groups: substituted or unsubstituted thienyl, furanyl, pyranyl, phenoxathiyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, indolyl, isoindolyl, indazolyl, purinyl, quinolizinyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, pteridinyl, carbazolyl, carboline, phenanthridinyl, phenanthrolinyl, acridinyl, phenazinyl, thiazolyl, phenothiazinyl, oxazolyl, phenoxazinyl, oxazolyl, oxadiazolyl, furazanyl, dithienopyrrolyl, trithienyl, benzoxazolyl, benzimidazolyl , benzothiophenyl, benzothiazolyl, benzothiophenyl, benzofuranyl, benzopyranyl, benzophenoxathiyl, benzopyrrolyl, benzimidazolyl, benzopyrazolyl, benzopyridinyl, benzopyrazinyl, benzopyrimidinyl, benzopyridazinyl, benzoindolizinyl, benzoindolyl, benzoindazolyl, benzopurinyl, benzoquinolizinyl, benzoquinolyl, benzophthalazinyl, benzonaphthyridinyl, benzoquinoxalinyl, benzopteridinyl, benzocarbazolyl, benzocarbolinyl, benzophenanthridinyl, benzophenanthrolinyl, benzoacridinyl, benzophenazinyl, benzothiazolyl, benzophenothiazinyl, benzoxazolyl, benzophenoxazinyl. Each of these substituents may be additionally substituted.

[0017] The alkylene group is selected from any one or a combination of the following groups: substituted or unsubstituted methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecanylene, octadecylene, nonadecanylene or eicosylene.

[0018] The heteroaryl group is selected from any one or a combination of the following groups: substituted or unsubstituted pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furanyl, benzofuranyl, isobenzofuranyl, quinolyl, 1-isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, o-diazophenanthrenyl, phenazinyl, phenothiazinyl, phenothiazinyl, phenoxazinyl, oxazolyl, furanyl or thienyl.

[0019] The cycloalkyl group is selected from any one or a combination of the following groups: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, 11-carbon cycloalkyl, 12-carbon cycloalkyl, 13-carbon cycloalkyl, 14-carbon cycloalkyl, 15-carbon cycloalkyl, 16-carbon cycloalkyl, 17-carbon cycloalkyl, 18-carbon cycloalkyl, 19-carbon cycloalkyl or 20-carbon cycloalkyl, which may or may not contain a substituent.

[0020] The substituent is selected from any one or a combination of the following groups: an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a heterocyclic group (the heteroatom group contained therein is selected from B, Si, Sn, Ge, N, O, S, Se, Zr), a heteroaryl group, an aralkyl group or an aralkyloxy group having 1 to 30 carbon atoms.

[0021] As a preferred embodiment, the fused-ring aromatic imide derivative of naphthalene imide and pyrene alternately fused in the present invention is a compound having the following structure:

[0022]

[0023]

[0024] The present invention also provides the use of the condensed-ring aromatic imide derivatives formed by alternately condensing naphthylimide and pyrene as light-absorbing materials and electron-transmitting materials in organic field-effect transistors and organic solar cells.

[0025] The present invention further provides a method for preparing the condensed-ring aromatic imide derivatives of naphthylimide and pyrene alternately fused, the method has short synthesis steps, mild conditions, simple operation, convenient and readily available raw materials, and is easy for industrial production.

[0026] The method for preparing the condensed-ring aromatic imide derivative of naphthalene imide and pyrene alternately fused in the present invention comprises the following steps:

[0027] 1) tetrabromonaphthalene diimide represented by formula (a) and heteroatom-fused fused-ring aromatic imide derivative represented by formula (b) are charged into a reactor;

[0028]

[0029] 2) Under the protection of inert gas, first add palladium catalyst, ligand, base and oxidant into the reactor in step 1), then add organic solvent, and stir and heat the solution to 50-130° C.;

[0030] 3) reacting for 0.5 to 8 hours, and obtaining the condensed-ring aromatic imide derivative in which the naphthylimide and pyrene are alternately fused through post-treatment.

[0031] In step 1), the heteroatom-fused fused ring aromatic imide derivative is a unilateral heteroatom-fused fused ring aromatic imide derivative (structure shown in formula b1) or a bilateral heteroatom-fused fused ring aromatic imide derivative (structure shown in formula b2); wherein the heteroatom M is selected from any one of the four heteroatoms of Si, Ge, Sn, and Zr, and M are the same or different;

[0032]

[0033] Among them, R in formula (b1) and formula (b2) 2 R in claim 1 2 The same; R in formula (a), (b1) and (b2) 1 R in claim 1 1 same.

[0034] Taking the compound represented by formula (a) as 1 equivalent, the equivalent ratio of the palladium catalyst is 0.01-4, preferably 0.05-3; the equivalent ratio of the ligand is 0.01-20, preferably 0.05-10; the equivalent ratio of the base is 2-15, preferably 2-12; the equivalent ratio of the oxidant is 0.1-15, preferably 0.5-12; the equivalent ratio of the compound represented by formula (b1) or formula (b2) is 0.3-5, preferably 0.5-3.

[0035] The raw materials used in the present invention can be purchased from the market or synthesized according to the prior art. For example, the tetrabromonaphthalene diimide shown in formula (a) is synthesized according to the method reported in the literature (J. Org. Chem. 2007, 72, 21, 8070-8075; Org. Lett., 2007, 9, 3917-3920.). The heteroatom-fused condensed ring aromatic imide derivative shown in formula (b) is obtained by naphthalene diimide substituted with boric acid or boric acid ester, or naphthalene diimide substituted with tin, and heteroatom-fused dibromo-substituted biphenyl undergoing Suzuki coupling and CH bond transfer reaction or Stille coupling and CH bond transfer reaction.

[0036] In the above preparation method, the compound represented by formula (a) is taken as 1 equivalent, the equivalent ratio of the palladium catalyst is 0.01 to 4, preferably 0.05 to 3; the equivalent ratio of the ligand is 0.01 to 20, preferably 0.05 to 10; the equivalent ratio of the base is 2 to 15, preferably 2 to 12; the equivalent ratio of the oxidant is 0.1 to 15, preferably 0.5 to 12; the equivalent ratio of the compound represented by formula (b) is 0.3 to 5, preferably 0.5 to 3.

[0037] In the above preparation method, the palladium catalyst in step 1) is selected from palladium acetate (Pd(OAc) 2 ), bis(tri-tert-butylphosphine)palladium(0), Pd(P(t-Bu) 3 ) 2 ), tetrakis(triphenyl phosphine)palladium,Pd(PPh 3 ) 4 ), bis(triphenylphosphine)palladium(II)dichloride, Pd(PPh 3 ) 2 Cl 2 ), palladium chloride (PdCl 2 ), [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II), Pd(dppf)Cl 2 ), palladium(II)trifluoroacetate, Pd(CF 3 CO 2 ) 2), bis(dibenzylideneacetone)palladium-tricyclohexylphosphine (Pd(dba) 2 -PCy 3 ), tetrakis(acetonitrile)palladium(II)tetrafluoroborate, Pd(CH 3 CN) 4 (BF 4 ) 2 )

[0038] In the above preparation method, the ligand described in step 1) is tricyclohexylphosphine, triphenylphosphine, tributylphosphine, trimethoxyphosphine, triphenylarsenic, sodium hexafluoroantimonate, potassium hexafluoroantimonate, lithium hexafluoroantimonate, silver hexafluoroantimonate, tetraphenylphosphine hexafluoroantimonate, nitroso hexafluoroantimonate, (hexafluoroantimonate) triacetonitrile (pentamethylcyclopentadienyl) rhodium (III), and the ligand is added or not.

[0039] In the above preparation method, the base described in step 1) is one or more of sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide, potassium acetate, sodium acetate, potassium carbonate, sodium carbonate, cesium fluoride, potassium fluoride, tetrabutylammonium fluoride, cesium carbonate, potassium bicarbonate, sodium bicarbonate, sodium methoxide, sodium isopropoxide, potassium phosphate, sodium hydroxide, potassium hydroxide, triethylamine, titanium hydroxide, and barium hydroxide. The base can be added or not.

[0040] In the above preparation method, the oxidant described in step 1) is one or more of p-benzoquinone, o-benzoquinone, tetrafluoro-1,4-benzoquinone, p-tetrachlorobenzoquinone, o-tetrachlorobenzoquinone, p-tetrabromobenzoquinone, o-tetrabromobenzoquinone, and 2,3-dichloro-5,6-dicyano-p-benzoquinone, and the oxidant can be added or not.

[0041] In the above preparation method, the organic solvent described in step 2) is selected from any one of benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, acetonitrile, 1,4-dioxane, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-dimethylformamide, dichloromethane, dichloroethane, trichloromethane, 1,1,2,2-tetrachloroethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethanol, acetic acid, acetic anhydride, ethyl acetate, diisopropylamine, triethylamine, n-butanol, isopropanol, and carbon tetrachloride.

[0042] In the above preparation method, the post-treatment is: cooling, filtering, concentrating the filtrate, and separating and purifying.

[0043] In a preferred embodiment, the following synthetic route is used to synthesize the condensed ring aromatic imide derivatives of naphthylimide and pyrene alternately fused as shown in formula (1) and (2):

[0044]

[0045] In another preferred embodiment, the synthetic route for synthesizing the condensed-ring aromatic imide derivatives of naphthylimide and pyrene alternately fused as shown in formula (3), (4) and (5) is as follows:

[0046]

[0047] The compound obtained by the present invention is analyzed by nuclear magnetic resonance spectrum ( 1 H-NMR, 13 C-NMR and high resolution mass spectrometry (HRMS) confirmed the above structure.

[0048] The beneficial effects of the present invention are:

[0049] (1) The condensed ring aromatic imide derivatives of naphthylimide and pyrene alternately fused provided by the present invention are prepared in one step by using tetrabromonaphthalene diimide and heteroatom condensed ring aromatic imide derivatives as raw materials, and by palladium catalysis under the protection of inert gas to undergo aromatization reaction. The condensed ring aromatic imide derivatives of naphthylimide and pyrene alternately fused have strong absorption of visible light with a wavelength of about 400-700nm and have a high fluorescence quantum yield; TGA test shows that the thermal decomposition temperature of the derivatives is greater than 340°C, indicating that the derivatives have good chemical stability and can be used as organic semiconductor n-type electron transport materials in organic field effect tubes, solar cell materials, liquid crystal materials, organic light-emitting materials and industrial dyes.

[0050] (2) The method of the present invention uses readily available raw materials, has short synthesis steps, mild conditions, simple operation, and is easy to industrialize. DETAILED DESCRIPTION

[0051] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0052] Example 1

[0053] This embodiment provides a condensed-ring aromatic imide derivative in which N,N'-di(2,6-diisopropylphenyl) unilaterally dibromo-substituted [2+1] naphthalene imide and pyrene are alternately fused, and the synthesis route thereof is as follows:

[0054]

[0055] The specific synthesis steps of the condensed-ring aromatic imide derivatives of naphthalene imide and pyrene alternately fused in this embodiment are as follows:

[0056] (1) To a reaction bottle containing 500 mg of unilateral tin atom-fused naphthalene imide, 510 mg of tetrabromonaphthalene imide, 29 mg of di(tri-tert-butylphosphine)palladium, and 430 mg of cesium fluoride were added;

[0057] (2) Under nitrogen protection, inject 10 ml of tetrahydrofuran into the mixture prepared in step (1) and stir at 70°C;

[0058] (3) After reacting for 8 hours, the mixture was cooled and poured into water, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified by silica gel column chromatography to obtain 500 mg of a red powder of N,N'-di(2,6-diisopropylphenyl) unilaterally dibromo-substituted [2+1] naphthaleneimide and pyrene alternately fused fused aromatic imide derivatives with a yield of 60%. 1 HNMR (400MHz, CD 2 Cl 2 ,298K,ppm): δ=8.93(s,2H),8.51-8.46(m,4H),7.53-7.50(t,4H),7.40-7.36(m,10H),2.83(s,8H),1.19(t,48H); 13 CNMR (100MHz, CD 2 Cl 2 , 298K): δ=158.6,143.0,141.3,139.7,136.9,136.5,132.0,131.8,130.4,130.4,130.3,130.3,127. 4,127.2,126.3,124.2,123.8,123.8,123.5,122.4,28.4,23.3; HRMS(MALDI(N),100%)m / zcalcdforC 88 H 76 Br 2 N 4 O 8 :1474.4031,found:1474.4036.

[0059] TGA testing shows that its thermal decomposition temperature is greater than 346°C, indicating that it has good chemical stability.

[0060] Example 2

[0061] This embodiment provides a fused-ring aromatic imide derivative in which N,N'-di(1-pentylhexyl)-substituted [3+2] naphthalene imide and pyrene are alternately fused, and the synthesis route thereof is as follows:

[0062]

[0063] The specific synthesis steps of the condensed ring aromatic imide derivatives described in this embodiment are as follows:

[0064] (1) To a reaction bottle containing 500 mg of unilateral tin atom-fused naphthalene imide, 254 mg of tetrabromonaphthalene imide, 29 mg of di(tri-tert-butylphosphine)palladium, and 436 mg of cesium fluoride were added;

[0065] (2) Under nitrogen protection, inject 10 ml of tetrahydrofuran into the mixture prepared in step (1) and stir at 70°C;

[0066] (3) After reacting for 16 hours, the mixture was cooled and poured into water, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified by silica gel column chromatography to obtain 462 mg of a red powder of N,N'-di(1-pentylhexyl)-substituted [3+2] naphthaleneimide and pyrene-alternatingly fused fused aromatic imide derivatives with a yield of 40%. 1 HNMR (400MHz, CD 2 Cl 2 ,298K,ppm): δ=8.90(s,4H),8.52-8.47(m,8H),7.33(m,4H),3.54(m,4H),2.90(m,2H),1.53(m,32H),1.29-1.27(m,64H),0.90(m,36H); 13 CNMR (100MHz, CD 2 Cl 2 , 298K): δ=163.4,163.1,162.9,146.3,145.9,139.5,135.0,134.8,131.4,130.8,129.7,127.9,127.4,127.2,126.8,126.4,12 5.0,124.2,121.5,120.8,55.3,54.9,32.5,32.3,31.8,31.6,26.7,26.5,22.5,14.1,13.9; HRMS(MALDI(N),100%)m / zcalcdfor C 132 H154 N 6 O 12 :2015.1625,found:2015.1621.

[0067] TGA testing shows that its thermal decomposition temperature is greater than 340°C, indicating that it has good chemical stability.

[0068] Example 3

[0069] This embodiment provides a fused-ring aromatic imide derivative in which N,N'-di(1-pentylhexyl)tetrabromo-substituted [3+2] naphthalene imide and pyrene are alternately fused, and the synthesis route thereof is as follows:

[0070]

[0071] The specific synthesis steps of the condensed ring aromatic imide derivatives described in this embodiment are as follows:

[0072] (1) To a reaction bottle containing 250 mg of bilaterally tin-fused naphthalene imide, 378 mg of tetrabromonaphthalene imide, 22 mg of di(tri-tert-butylphosphine)palladium, and 325 mg of cesium fluoride were added;

[0073] (2) Under nitrogen protection, inject 10 ml of tetrahydrofuran into the mixture prepared in step (1) and stir at 70°C;

[0074] (3) After reacting for 16 hours, the mixture was cooled and poured into water, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified by silica gel column chromatography to obtain 208 mg of a red powder of N,N'-di(1-pentylhexyl)tetrabromo-substituted [3+2]naphthaleneimide and pyrene alternately fused fused ring aromatic imide derivative with a yield of 42%. 1 HNMR (400MHz, CD 2 Cl 2 ,298K,ppm): δ=8.64-8.49(m,8H),7.35(m,4H),3.56(m,4H),2.93(m,2H),1.57(m,32H),1.32-1.27(m,64H),0.97(m,36H); 13 CNMR (100MHz, CD 2 Cl 2, 298K): δ=163.5,163.3,163.0,146.7,146.1,139.8,135.3,134.8,131.4,130.8,129.7,127.9,127.4,127.2,126.8,126.4,12 5.0,124.2,121.7,120.6,55.5,54.6,32.5,32.3,31.8,31.6,26.7,26.5,22.5,14.1,13.9; HRMS(MALDI(N),100%)m / zcalcdforC 132 H 150 Br 4 N 6 O 12 :2026.8043,found:2026.8039.

[0075] TGA testing shows that its thermal decomposition temperature is greater than 340°C, indicating that it has good chemical stability.

[0076] Example 4

[0077] This embodiment provides a condensed-ring aromatic imide derivative in which N,N'-di(n-octyl)-substituted [5+4]naphthalene imide and pyrene are alternately fused, and the synthesis route thereof is as follows:

[0078]

[0079] The specific synthesis steps of the condensed ring aromatic imide derivative are as follows:

[0080] (1) To a reaction bottle containing 100 mg of bilaterally silicon-fused naphthalene imide, 284 mg of a unilaterally dibromo-substituted [2+1] naphthalene imide and pyrene-alternatingly fused fused aromatic imide derivative, 37 mg of palladium trifluoroacetate, and 57 mg of sodium hexafluoroantimonate were added;

[0081] (2) Under nitrogen protection, inject 10 ml of dichloroethane into the mixture prepared in step (1) and stir at 85° C.;

[0082] (3) After reacting for 16 hours, the mixture was cooled and poured into water, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified by silica gel column chromatography to obtain 121 mg of a dark blue powder of N,N'-di(n-octyl)-substituted [5+4]naphthaleneimide and pyrene-alternating fused fused aromatic imide derivatives with a yield of 36%. 1 HNMR (400MHz, CD 2 Cl 2,298K,ppm): δ=8.93(s,4H),8.57-8.46(m,16H),7.33(m,8H),3.55(m,20H),2.87(m,20H),1.53-1.30(m,100H),1.02(m,30H); 13 CNMR (100MHz, CD 2 Cl 2 , 298K): δ=163.4,163.1,162.9,146.3,145.9,139.5,135.0,134.8,131.4,130.8,129.7,127.9,127.4,127.2,126.8,126.4, 125.0,124.2,121.5,120.8,55.3,54.9,40.3,31.9,31.6,30.2,29.3,26.7,22.7,14.1; HRMS(MALDI(N),100%)m / zcalcdforC 198 H 198 N 10 O 20 :3035.4782,found:3035.4787.

[0083] TGA testing shows that its thermal decomposition temperature is greater than 340°C, indicating that it has good chemical stability.

[0084] Example 5

[0085] This embodiment provides a condensed ring aromatic imide derivative in which N,N'-di(n-octyl)-substituted [5+6] naphthalene imide and pyrene are alternately fused, and the synthesis route thereof is as follows:

[0086]

[0087] The specific synthesis steps of the condensed ring aromatic imide derivatives described in this embodiment are:

[0088] (1) Into a reaction bottle containing 100 mg of bilaterally silicon-fused naphthalene imide, 317 mg of a unilaterally dibromo-substituted [2+2] naphthalene imide and pyrene-alternatingly fused fused aromatic imide derivative, 37 mg of palladium trifluoroacetate, 79 mg of silver hexafluoroantimonate, and 136 mg of tetrachlorobenzoquinone were added;

[0089] (2) Under nitrogen protection, inject 10 ml of dichloroethane into the mixture prepared in step (1) and stir at 85° C.;

[0090] (3) After reacting for 16 hours, the mixture was cooled and poured into water, extracted with dichloromethane, concentrated, and the solvent was removed. The crude product was separated and purified by silica gel column chromatography to obtain 140 mg of a dark blue powder of N,N'-di(n-octyl)-substituted [5+6]naphthaleneimide and pyrene-alternating fused fused aromatic imide derivatives with a yield of 38%. 1 HNMR (400MHz, CD 2 Cl 2 ,298K,ppm): δ=8.93(m,16H),8.57-8.46(m,8H),7.67(m,8H),7.33(m,8H),3.62(m,20H),2.82(m,20H),1.53-1.30(m,100H),1.07(m,30H); 13 CNMR (100MHz, CD 2 Cl 2 , 298K): δ=163.6,163.1,162.9,146.3,145.9,140.0,135.0,134.8,133.1,132.5,131.4,130.8,128.7,127.9,127.4,127.2,126.8 ,126.4,125.9,123.8,119.5,55.3,54.9,42.3,40.3,31.9,31.6,30.2,29.3,26.7,22.7,14.1; HRMS(MALDI(N),100%)m / zcalcdforC 222 H 210 N 10 O 20 :3335.5724,found:3335.5726.

[0091] TGA testing shows that its thermal decomposition temperature is greater than 340°C, indicating that it has good chemical stability.

[0092] Experimental Example 1

[0093] This experimental example detects the application of the fused-ring aromatic imide derivatives of naphthylimide and pyrene alternately fused in the method of the present invention as organic semiconductor transmission materials in organic field effect transistors.

[0094] The condensed ring aromatic imide derivatives of [3+2] naphthalene imide and pyrene substituted by N,N'-di(1-pentylhexyl) and condensed ring aromatic imide derivatives substituted by [5+4] naphthalene imide and pyrene fused alternately obtained in Example 2 and Example 4 were used as the organic semiconductor part of the organic field effect transistor device to construct a bottom gate-top contact device structure, wherein the source and drain electrodes were 50 nm gold electrodes (evaporation method), the gate electrode was a gallium indium composite, and the insulating layer was OTS-modified SiO 2 / Si substrate. The organic semiconductor layer was prepared by spin coating with a thickness of 40-60nm and heated and annealed at 200°C. The solvent was chloroform with a concentration of 1mg / ml. All tests were carried out in air. The field effect mobility test results of the two materials are shown in Table 1.

[0095] Table 1 - Field effect mobility test results of two materials

[0096]

[0097]

[0098] Electron mobility μ e Indicates the mobility of electrons in semiconductors under different electric fields. e max It indicates the maximum mobility of electrons measured in semiconductors. on / I off V is the switching ratio, which indicates the switching performance of the device under a certain gate voltage. It is particularly important in matrix display and logic circuits. The larger the ratio of on-state current to off-state current, the better. t The threshold voltage refers to the voltage value at which the transistor starts to conduct when the difference between the gate voltage and the source voltage reaches a certain value during the operation of the field effect transistor.

[0099] It can be seen from Table 1 that the threshold voltage values ​​of this type of material are all less than 10 V. The preliminary test results of electron mobility, threshold voltage and switching ratio in the table show that this material has good electron transmission ability in the air and has the potential to be used as an electron acceptor material in organic optoelectronic devices.

[0100] Experimental Example 2

[0101] This experimental example tests the application of the fused-ring aromatic imide derivatives of the present invention, which are alternately fused with naphthalene imide and pyrene, as organic semiconductor n-type electron transport materials in organic solar cells.

[0102] The condensed ring aromatic imide derivatives of [3+2] naphthalene imide substituted by N,N'-di(1-pentylhexyl) and pyrene and the condensed ring aromatic imide derivatives of [3+2] naphthalene imide substituted by N,N'-di(1-pentylhexyl) tetrabromo and pyrene obtained in Examples 2 and 3 were used as acceptor materials for organic solar cells, and P3TEA was used as the donor material of the organic photoelectric layer to construct a bulk heterojunction organic solar device structure, and the inverted device structure was ITO / ZnO(30nm) / BHJ / MoO x (10nm) / Al, of which ZnO and MoO x The parameters of the solar cell device are shown in Table 2. The solvent used is o-xylene and the light source is AM1.5G (100 mWcm -2 ).

[0103] Table 2 - Solar cell device parameters

[0104]

[0105] Photovoltaic conversion efficiency (PCE) is a key indicator for measuring the performance of organic solar cells, indicating the percentage of incident light energy converted into electrical energy. Under a certain light intensity, PCE is proportional to V OC , J SC If you want to improve the efficiency of photovoltaic devices, you need to start by improving these three parameters. PCE ave is the average value of five devices. OC It is the voltage when the positive and negative electrodes of a solar cell are disconnected under light, that is, the maximum output voltage of the solar cell. In addition to the energy level of the active material, the microscopic morphology of the active layer, the ratio of donors to acceptors, the interface characteristics between the active layer and the electrode, and temperature also affect the V OC There is also a certain degree of influence. Short circuit current density J SC It is the current per unit area of ​​a solar cell when the positive and negative electrodes are short-circuited under light, that is, the maximum output current density of the battery. The size of Jsc is closely related to the light absorption capacity of the active layer, the generation of photogenerated charges, the mobility of carriers, etc. The fill factor FF is defined as the maximum output power P of a solar cell. max With V OC and J SC FF is mainly related to the carrier mobility of the active material, the transport and recombination of carriers, the morphology and thickness of the active layer, and the contact resistance of each interface.

[0106] It can be seen from Table 2 that the condensed aromatic imide derivative material of naphthylimide and pyrene alternately fused in the present invention as an acceptor material for organic solar cells has very strong absorption in the visible light region, so that the Jsc value of the prepared organic solar cell device is greater than 10 mA cm -2 , indicating that the organic solar cell device prepared based on the condensed-ring aromatic imide derivatives of the present invention, which are alternately fused with naphthalene imide and pyrene, has a high photocurrent density Jsc, and has a matching energy level and good film-forming property with common donor materials, and obtains a high open circuit voltage V OC and filling factor FF, achieving high photoelectric conversion efficiency, thus providing new materials for the development of light and flexible organic solar cells.

[0107] The present invention is not limited to the above-mentioned optimal implementation mode. Anyone can derive other various forms of products under the inspiration of the present invention. However, no matter what changes are made in the shape or structure, all technical solutions that are the same or similar to those of the present application fall within the protection scope of the present invention.

Claims

1. A condensed-ring aromatic imide derivative in which naphthalene imide and pyrene are alternately fused, characterized in that: The structure is shown in formula (I) or formula (II): Wherein: R1 is selected from any of the following groups: each independently represents hydrogen, a group containing a substituent or a group without a substituent, and the group is C 1-60 Alkyl, C 1-60 Alkoxy, C 3-60 Cycloalkyl, C 5-60 Aryl, C 1-60 Alkyl aryl, C 1-60 Alkyl heteroaryl, C 1-60 Alkyl heterocyclic group, C 1-60 Alkyleneoxyalkyl, C 1-60 Alkyleneoxyaryl, C 1-60 Alkyleneoxyheteroaryl or C 1-60 Alkyleneoxyheterocyclic group; R1 is the same or different; R2 is selected from any of the following groups: each independently represents hydrogen, halogen, a group containing or not containing a substituent, and the group is C 1-60 Alkyl, C 1-60 Alkoxy, C 3-60 Cycloalkyl, C 5-60 Aryl, C 1-60 Alkyl aryl, C 1-60 Alkyl heteroaryl, C 1-60 Alkyl heterocyclic group, C 1-60 Alkyleneoxyalkyl, C 1-60 Alkyleneoxyaryl, C 1-60 Alkyleneoxyheteroaryl, C 1-60 Alkyleneoxyheterocyclyl, cyclopentadienyl, cyclopentadienyl or 2,2′-biphenyl, R2 are the same or different; The aromatic groups Ar on both sides in formula (II) are selected from any of the following groups: the aromatic groups are selected from phenyl, cyclopentadienyl, cyclopentadienyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, tetraphenyl, pentphenyl, hexaphenyl, pyrenyl, indenyl, fluorenyl or heteroaryl groups which may contain or not contain substituents.

2. The condensed-ring aromatic imide derivative of naphthylimide and pyrene alternately fused according to claim 1, characterized in that: The alkyl group is selected from any one or a combination of the following groups: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl or eicosyl, which may or may not contain a substituent.

3. The fused-ring aromatic imide derivative of naphthylimide and pyrene alternately fused according to claim 1, characterized in that: The alkoxy group is selected from any one or a combination of the following groups: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanyloxy, octadecyloxy, nonadecanyloxy or eicosyloxy, which may or may not contain a substituent; The heterocyclic group is selected from any one or a combination of the following groups: substituted or unsubstituted thienyl, furanyl, pyranyl, phenoxathiyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, indolyl, isoindolyl, indazolyl, purinyl, quinolizinyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, pteridinyl, carbazolyl, carboline, phenanthridinyl, phenanthrolinyl, acridinyl, phenazinyl, thiazolyl, phenothiazinyl, oxazolyl, phenoxazinyl, oxazolyl, oxadiazolyl, furazanyl, dithienopyrrolyl, trithienyl, benzoxazolyl, benzimidazolyl , benzothiophenyl, benzothiazolyl, benzothiophenyl, benzofuranyl, benzopyranyl, benzophenoxathiyl, benzopyrrolyl, benzimidazolyl, benzopyrazolyl, benzopyridinyl, benzopyrazinyl, benzopyrimidinyl, benzopyridazinyl, benzoindolizinyl, benzoindolyl, benzoindazolyl, benzopurinyl, benzoquinolizinyl, benzoquinolyl, benzophthalazinyl, benzonaphthyridinyl, benzoquinoxalinyl, benzopteridinyl, benzocarbazolyl, benzocarbolinyl, benzophenanthridinyl, benzophenanthrolinyl, benzoacridinyl, benzophenazinyl, benzothiazolyl, benzophenothiazinyl, benzoxazolyl, benzophenoxazinyl; The alkylene group is selected from any one or a combination of the following groups: substituted or unsubstituted methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecanylene, octadecylene, nonadecanylene or eicosylene.

4. The fused-ring aromatic imide derivative of naphthylimide and pyrene alternately fused according to claim 1, characterized in that: The aryl group is selected from any one or a combination of the following groups: phenyl, cyclopentadienyl, cyclopentadienyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, tetraphenyl, pentacene, hexaphenyl, pyrenyl, indenyl or fluorenyl, which may or may not contain a substituent.

5. The fused-ring aromatic imide derivative of naphthalene imide and pyrene alternately fused according to claim 1, characterized in that: The heteroaryl group is selected from any one or a combination of the following groups: substituted or unsubstituted pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furanyl, benzofuranyl, isobenzofuranyl, quinolyl, 1-isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, o-diazophenanthrenyl, phenazinyl, phenothiazinyl, phenothiazinyl, phenoxazinyl, oxazolyl, furanyl or thienyl.

6. The fused-ring aromatic imide derivative of naphthylimide and pyrene alternately fused according to claim 1, characterized in that: The cycloalkyl group is selected from any one or a combination of the following groups: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, 11-carbon cycloalkyl, 12-carbon cycloalkyl, 13-carbon cycloalkyl, 14-carbon cycloalkyl, 15-carbon cycloalkyl, 16-carbon cycloalkyl, 17-carbon cycloalkyl, 18-carbon cycloalkyl, 19-carbon cycloalkyl or 20-carbon cycloalkyl, which may or may not contain a substituent.

7. The condensed-ring aromatic imide derivative of naphthalene imide and pyrene alternately fused according to any one of claims 1 to 6, characterized in that: The substituent is selected from any one or a combination of the following groups: an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a heterocyclic group, a heteroaryl group, an aralkyl group or an aralkyloxy group having 1 to 30 carbon atoms.

8. Use of the condensed-ring aromatic imide derivative of naphthalene imide and pyrene alternately fused according to any one of claims 1 to 7, characterized in that: The application is to use the material as a light absorbing material or an electron transporting material in an organic field effect transistor, an organic electroluminescent device, an organic thermochromic element or an organic solar cell.

9. The method for preparing the condensed-ring aromatic imide derivative of naphthalene imide and pyrene alternately fused according to any one of claims 1 to 7, characterized in that: The steps include: 1) tetrabromonaphthalene diimide and a heteroatom-fused fused-ring aromatic imide derivative represented by formula (a) are charged into a reactor; 2) Under the protection of inert gas, first add palladium catalyst, ligand, base and oxidant into the reactor in step 1), then add organic solvent, and stir and heat the solution to 50-130° C.; 3) reacting for 0.5 to 8 hours, and obtaining the condensed-ring aromatic imide derivative in which the naphthylimide and pyrene are alternately fused through post-treatment.

10. The preparation method according to claim 9, characterized in that: In step 1), the heteroatom-fused fused ring aromatic imide derivative is a unilateral heteroatom-fused fused ring aromatic imide derivative represented by formula (b1) or a bilateral heteroatom-fused fused ring aromatic imide derivative represented by formula (b2); wherein the heteroatom M is selected from any one of the four heteroatoms of Si, Ge, Sn, and Zr, and M are the same or different; Wherein, R2 in formula (b1) and formula (b2) is the same as R2 in claim 1; R1 in formula (a), (b1) and (b2) is the same as R1 in claim 1; Taking the compound represented by formula (a) as 1 equivalent, the equivalent ratio of the palladium catalyst is 0.01-4, preferably 0.05-3; the equivalent ratio of the ligand is 0.01-20, preferably 0.05-10; the equivalent ratio of the base is 2-15, preferably 2-12; the equivalent ratio of the oxidant is 0.1-15, preferably 0.5-12; the equivalent ratio of the compound represented by formula (b1) or formula (b2) is 0.3-5, preferably 0.5-3.

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