Heteroatom condensed fused ring aryl imide derivative as well as preparation method and application thereof

Abstract

The invention discloses a heteroatom condensed ring aryl imide derivative and a preparation method and application thereof, and the heteroatom condensed ring aryl imide derivative is prepared by using mono-boric acid ester group substituted or diboric acid ester group substituted-1, 4: 5, 8-naphthalimide, mono-boric acid group substituted or diboric acid group substituted-1, 4: 5, 8-naphthalimide, mono-tin group substituted or ditin group substituted-1, 4: 5, 8-naphthalimide or mono-tin group substituted or ditin group substituted-1, 4: 5, 8-naphthalimide. The heteroatom-condensed condensed ring aryl imide derivative is prepared by taking 1, 8-naphthalimide and heteroatom-condensed dibromo-substituted biphenyl as raw materials through a one-step method, has relatively strong absorption on visible light with the wavelength of about 400-700nm, has relatively high fluorescence quantum yield and good chemical stability, and can be applied to the field of fluorescence imaging. The compound can be used as an organic semiconductor n-type electron transport material to be applied to an organic field effect transistor, an organic electroluminescent device, an organic thermochromic element, an organic solar cell and the like, and can also be used as an intermediate to prepare a novel fused ring aromatic imide electron acceptor material.

Description

Technical Field

[0001] The invention belongs to the technical field of organic photoelectric materials, and specifically relates to a heteroatom fused fused ring aromatic imide derivative 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] By modifying the naphthalene core of naphthaleneimide, the solid-state stacking state, solubility and optoelectronic properties of the molecule can be significantly regulated. Therefore, modification of the naphthalene core, especially the introduction of heteroatom fused ring systems, has been a hot topic in the study of naphthaleneimide chemistry in recent years.

[0004] Naphthalene imide containing heteroatom fused rings, i.e., heteroatom fused fused ring aromatic imide derivative conjugated system, has important applications in organic optoelectronic materials, such as conjugated systems based on heteroatom fused rings containing silicon (Si), germanium (Ge), tin (Sn), and zirconium (Zr). The d orbitals of these four types of heteroatoms produce a conjugated effect with the orbitals of the butadiene part, effectively reducing the energy of the lowest unoccupied orbital (LUMO) of this type of material, improving the electron affinity and conductivity, and facilitating the transmission of electrons. The electronic effects of these four types of heteroatoms are introduced into the conjugated structure, and the heteroatoms are used to construct rigid ladder-shaped conjugated molecules. The combination of the two effects makes the heteroatom fused fused ring aromatic imide derivatives have good thermal stability, adjustable photophysical properties and high fluorescence efficiency, and have great application prospects in organic light-emitting diodes, polymer solar cells, organic field effect transistors, organic thermochromic devices, etc. The introduction of heteroatom structures can also effectively regulate the optical properties of molecules.

[0005] Traditional synthesis of molecules containing heteroatom fused ring structures involves organic lithium reagents and Grignard reagents, which are not suitable for reaction substrates containing carbonyl groups and have a narrow tolerance range for functional groups. Although there have been reports of carbonyl compounds with heteroatom fused ring structures recently, their synthesis methods are all through first adding a single bond, and then oxidative deprotonation and dearomatization on the heteroatom. The route is too long and will inevitably lead to a low yield of the final product. In addition, the presence of electron-withdrawing groups such as carbonyl makes oxidative deprotonation reactions more difficult to carry out than electron-rich systems, and is generally not suitable for compounds with electron-deficient systems. Naphthalene imide happens to be an electron-deficient system. Therefore, traditional methods cannot be applied to the synthesis of naphthalene imide structures containing heteroatom fused rings. Summary of the invention

[0006] In order to solve the above problems existing in the prior art, the present invention provides a heteroatom-fused fused ring aromatic imide derivative and a preparation method and application thereof. The present invention uses naphthalene imide as a raw material to prepare a heteroatom-fused fused ring aromatic imide derivative in a one-step method. The heteroatom-fused fused ring aromatic imide derivative can be used as an organic semiconductor n-type electron transport material in organic field effect transistors, organic electroluminescent devices, organic thermochromic elements, organic solar cells, etc., and can also be used as an intermediate to prepare a new type of fused ring aromatic imide electron acceptor material.

[0007] The technical solution adopted by the present invention is:

[0008] A heteroatom-fused fused-ring aromatic imide derivative, the structure of which is shown in formula (I) or formula (II):

[0009]

[0010] 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 are the same or different;

[0011] M is selected from any one of the following four heteroatoms: Si (silicon), Ge (germanium), Sn (tin), Zr (zirconium), and M is the same or different;

[0012] R2 is selected from any of the following groups: each independently represents hydrogen, a group containing a substituent or a group without 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 1-60an alkyleneoxy heterocyclic group, a cyclopentadienyl group, a cyclopentadienyl group or a 2,2'-biphenyl group, wherein R2 are the same or different.

[0013] Preferably, the heteroatom-fused fused-ring aromatic imide derivative of the present invention is a compound having the following structure:

[0014]

[0015]

[0016] 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;

[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 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.

[0019] 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;

[0020] 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.

[0021] 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.

[0022] The heterocyclic group is selected from any one or a combination of the following groups: thienyl, furanyl, pyranyl, phenoxathiyl, pyrrolyl, imidazolyl, pyrazolyl, pyridinyl, 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, benzo Thiazolyl, benzothienyl, 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, or a group derived from the ring of the above groups fused with the ring of the aryl group.

[0023] The R1 is selected from any one or a combination of the following groups: each independently represents hydrogen, C with or without a substituent; 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;

[0024] The R2 is selected from any one or a combination of the following groups: independently representing hydrogen, alkyl, alkoxy, cycloalkyl, aryl, alkylaryl, alkylheteroaryl, alkylheterocyclic, alkyleneoxyalkyl, alkyleneoxyaryl, alkyleneoxyheteroaryl, alkyleneoxyheterocyclic, cyclopentadienyl, cyclopentadienyl, biphenyl, preferably C 1-60 Alkyl, C 1-60 Alkoxy, C 5-60 Aryl, C 3-60 Cycloalkyl, cyclopentadienyl, cyclopentadienyl, 2,2'-biphenyl.

[0025] 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.

[0026] The heteroatom-fused fused-ring aromatic imide derivative is used in any of the following applications:

[0027] (1) Application as light absorbing material or electron transport material in organic field effect transistors, organic electroluminescent devices, organic thermochromic elements or organic solar cells;

[0028] (2) Application as intermediates in the preparation of novel condensed-ring aromatic imide derivative electron acceptor materials.

[0029] The method for preparing the heteroatom-fused fused-ring aromatic imide derivative is characterized by comprising the following steps:

[0030] 1) placing mono-boric acid ester substituted or di-boric acid ester substituted 1,4:5,8-naphthalene diimide represented by formula (a1), mono-boric acid substituted or di-boric acid substituted 1,4:5,8-naphthalene diimide represented by formula (a2), or mono-tin substituted or di-tin substituted 1,4:5,8-naphthalene diimide represented by formula (a3) ​​into a reactor;

[0031]

[0032] 2) Under nitrogen or argon protection, add any compound represented by formula (b) into the reactor in step 1), then add palladium catalyst, ligand, base and organic solvent, and stir and heat the solution to 50-130° C.;

[0033]

[0034] 3) reacting for 5 to 24 hours, and obtaining the heteroatom-fused fused-ring aromatic imide derivative through post-treatment;

[0035] Among them, R2 in formula (a3) ​​and formula (b) is the same as R2 in claim 1; R1 in formula (a1), (a2) and (a3) ​​is the same as R1 in claim 1.

[0036] Taking the compound represented by formula (a) as 1 equivalent, the equivalent ratio of the palladium catalyst is 0.01 to 4, preferably 1 to 3; the equivalent ratio of the ligand is 0.01 to 20, preferably 0.01 to 10; the equivalent ratio of the base is 2 to 15, preferably 2 to 12; the equivalent ratio of the compound represented by formula (b) is 1 to 5, preferably 1 to 3.

[0037] The method of the invention has short synthesis steps, mild conditions, simple operation, readily available raw materials and is easy for industrial production.

[0038] The raw materials used in the present invention can be purchased from the market or synthesized according to the prior art, such as borate substituted and tin substituted naphthalene diimide are synthesized according to the method reported in the literature (Chem. Commun., 2014, 50, 13837; J. Am. Chem. Soc., 2012, 134, 5770-5773.). The borate substituted naphthalene diimide is obtained by adding an acid to the borate substituted naphthalene diimide.

[0039] In the above preparation method, the palladium catalyst described in step 1) is selected from one or more of palladium acetate (Pd(OAc)2), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), bis(triphenylphosphine)palladium(II)dichloride (Pd(PPh3)2Cl2), [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (II), Pd(dppf)Cl2), palladium chloride (PdCl2), bis(dibenzylideneacetone)palladium-tricyclohexylphosphine (bis(dibenzylideneacetone)dipalladium-tricyclohexylphosphine, Pd(dba)2-PCy3), and palladium on carbon (Pd / C).

[0040] In the above preparation method, the ligand described in step 1) is cuprous iodide, cupric iodide, cuprous bromide, cupric bromide, cuprous chloride, cupric chloride, tricyclohexylphosphine, triphenylphosphine, tributylphosphine, trimethoxyphosphine, triphenylarsine, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl, 1,4-bis(diphenylphosphino)propane, and the ligand is added or not.

[0041] 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.

[0042] In the above preparation method, the organic solvent described in step 2) is selected from one or more of toluene / ethanol / water, toluene / water, xylene / ethanol / water, xylene / water, tetrahydrofuran / ethanol / water, tetrahydrofuran / water, acetonitrile / water, 1,4-dioxane / water, N,N-dimethylacetamide / water, dimethyl sulfoxide / water, N,N-dimethylformamide / water, N,N-dimethylacetamide / water, dichloromethane / water, chloroform / water, ethanol / water, and ethylene glycol dimethyl ether / water.

[0043] In the above preparation method, the post-treatment is: cooling, filtering, concentrating the filtrate, and separating and purifying.

[0044] In a preferred embodiment, the synthesis of the heteroatom-fused fused-ring aromatic imide derivative represented by formula (I) adopts the following synthesis route:

[0045]

[0046] In another preferred embodiment, the heteroatom-fused fused-ring aromatic imide derivative represented by formula (II) is synthesized by the following synthetic route:

[0047]

[0048] 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.

[0049] The heteroatom-fused fused-ring aromatic imide derivative of the present invention can be used as an n-type electron transport material and applied to organic field effect transistors, solar cell materials, liquid crystal materials, organic luminescent materials, industrial dyes and the like.

[0050] The beneficial effects of the present invention are:

[0051] (1) The heteroatom-fused fused ring aromatic imide derivative provided by the present invention is prepared in one step by using mono-boronate-substituted or di-boronate-substituted-1,4:5,8-naphthalene diimide, or mono-boric acid-substituted or di-boric acid-substituted-1,4:5,8-naphthalene diimide, or mono-tin-substituted or di-tin-substituted-1,4:5,8-naphthalene diimide as raw materials, and subjecting them to Suzuki coupling and CH bond transfer reaction or Stille coupling and CH bond transfer reaction with heteroatom-fused dibromo-substituted biphenyl under the protection of inert gas and by palladium catalysis. The heteroatom-fused condensed ring aromatic imide derivatives of the present invention 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 transistors, organic electroluminescent devices, organic thermochromic elements, organic solar cells, etc., and can also be used as an intermediate to prepare new condensed ring aromatic imide electron acceptor materials.

[0052] (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

[0053] 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.

[0054] Example 1

[0055] This embodiment provides a N,N'-di(2,6-diisopropylphenyl)-substituted unilateral silicon atom-fused fused ring aromatic imide derivative, and its synthesis route is as follows:

[0056]

[0057] The specific synthesis steps of the N,N'-di(2,6-diisopropylphenyl)-substituted unilateral silicon atom-fused fused ring aromatic imide derivative are as follows:

[0058] (1) Add 330 mg of dibromo-substituted silicon-fused biphenyl, 82 mg of tetrakistriphenylphosphine palladium and 485 mg of potassium carbonate to a reaction bottle containing 500 mg of monoboron ester-substituted N,N'-2,6-diisopropylphenyl-naphthalene diimide;

[0059] (2) Under nitrogen protection, inject 10 ml of tetrahydrofuran and 2 ml of water into the mixture prepared in step (1), and stir at 80° C.;

[0060] (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 345 mg of a red powder of N,N'-di(2,6-diisopropylphenyl)-substituted unilateral silicon atom-fused condensed aromatic imide derivative with a yield of 60%.

[0061] The structure of the obtained derivative was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 8.90 (s, 2H), 8.25 (d, 2H), 7.80 (d, 2H), 7.55-7.50 (t, 2H),7.43-7.35(d,4H),7.28(t,2H),2.94-2.89(m,4H),1.26-1.22(m,24H),1.06(t,10H); 13 C NMR (100MHz, CD2Cl2, 298K): δ=158.6,146.0,141.3,139.5,136.29,136.3,135.3,133.4,133.4,131. 8,129.6,128.2,126.9,126.2,125.3,123.5,121.6,28.4,23.3,12.3,6.9; HRMS(MALDI(N),100%)m / z calcd for C 54 H 52 N2O4Si: 820.3696, found: 820.3692.

[0062] TGA testing showed that the thermal decomposition temperature of the obtained derivative was greater than 346°C, indicating that it has good chemical stability.

[0063] Example 2

[0064] This embodiment provides an N,N'-di(n-octyl)-substituted unilateral tin atom-fused fused ring aromatic imide derivative, and its synthesis route is as follows:

[0065]

[0066] The specific synthesis steps of the N,N'-di(n-octyl)-substituted unilateral tin atom-fused fused ring aromatic imide derivative are as follows:

[0067] (1) To a reaction bottle containing 500 mg of monoboronic acid-substituted N,N'-di(n-octyl)-substituted-naphthalene diimide, 515 mg of dibromo-substituted tin-fused biphenyl, 66 mg of bis(triphenylphosphine)palladium dichloride and 496 mg of sodium carbonate were added;

[0068] (2) Under nitrogen protection, inject 10 ml of toluene and 2 ml of water into the mixture prepared in step (1), and stir at 110° C.;

[0069] (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 490 mg of a red powder of N,N'-di(n-octyl)-substituted unilateral tin atom-fused condensed aromatic imide derivative with a yield of 67%.

[0070] The structure of the obtained derivative was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 9.01 (s, 2H), 8.75 (d, 2H), 7.92 (d, 2H), 7.59-7.53 (t, 2H) ,7.50-7.43(d,4H),7.26(t,2H),3.14(t,4H),1.67(m,4H),1.28-1.26(m,20H),0.96(m,12H); 13 C NMR (100MHz, CD2Cl2, 298K): δ=159.3,146.0,139.5,135.3,133.4,128.3,128.2,126.6,126.3,12 5.3,122.0,121.6,40.3,31.9,30.2,29.3,29.3,26.7,22.7,14.1,1.5; HRMS(MALDI(N),100%)m / z calcd for C 44 H 48 N2O4Sn: 788.2636, found: 788.2632.

[0071] TGA testing showed that the thermal decomposition temperature of the obtained derivative was greater than 340°C, indicating that it has good chemical stability.

[0072] Example 3

[0073] This embodiment provides a N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted unilateral germanium atom-fused fused ring aromatic imide derivative, and its synthesis route is as follows:

[0074]

[0075] The specific synthesis steps of the N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted unilateral germanium atom-fused fused ring aromatic imide derivative are as follows:

[0076] (1) Add 287 mg of dibromo-substituted germanium-fused biphenyl, 63 mg of tetrakistriphenylphosphine palladium and 21 mg of cuprous iodide to a reaction bottle containing 500 mg of monotin-substituted N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted naphthalene diimide;

[0077] (2) Under nitrogen protection, inject 10 ml of toluene into the mixture prepared in step (1) and stir at 110° C.;

[0078] (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 310 mg of a red powder of N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted unilateral germanium atom-fused condensed aromatic imide derivatives with a yield of 63%.

[0079] The structure of the obtained derivative was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 8.97 (s, 2H), 8.86 (d, 2H), 7.98 (d, 2H), 7.65-7.53 (t, 2H), 3.54 (t, 4H), 1.53 (m, 4H), 1.24-1.20 (m, 6H); 13 C NMR (100MHz, CD2Cl2, 298K): δ=159.3,146.0,139.5,135.3,133.4,128.3,128.2,126.6,126.3 ,125.3,122.0,122.0,120.2,120.2,118.2,103.1,40.1,22.9,7.6; HRMS(MALDI(N),100%)m / z calcd for C 38 H 22 F 14 GeN2O4: 910.0568, found: 910.0572.

[0080] TGA testing showed that the thermal decomposition temperature of the obtained derivative was greater than 348°C, indicating that it has good chemical stability.

[0081] Example 4

[0082] This embodiment provides an N,N'-di(1-pentylhexyl)-substituted unilateral zirconium atom-fused fused ring aromatic imide derivative, and its synthesis route is as follows:

[0083]

[0084] The specific synthesis steps of the N,N'-di(1-pentylhexyl)-substituted unilateral zirconium atom-fused fused ring aromatic imide derivative are as follows:

[0085] (1) To a reaction bottle containing 500 mg of monotin-substituted N,N'-di(1-pentylhexyl)-substituted naphthalene diimide, 368 mg of dibromo-substituted zirconium-fused biphenyl, 67 mg of tetrakistriphenylphosphine palladium and 22 mg of cuprous iodide were added;

[0086] (2) Under nitrogen protection, inject 10 ml of toluene into the mixture prepared in step (1) and stir at 115° C.;

[0087] (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 327 mg of a red powder of N,N'-di(1-pentylhexyl)-substituted unilateral zirconium atom-fused condensed aromatic imide derivative with a yield of 60%.

[0088] The structure of the obtained derivative was confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 8.97 (s, 2H), 8.86 (d, 2H), 7.98 (d, 2H), 7.65-7.53 (t, 2H) ,6.50-6.40(m,8H),3.54(m,2H),2.90(m,2H),1.53(m,8H),1.29-1.27(m,24H),0.90(m,12H); 13 C NMR (100MHz, CD2Cl2, 298K): δ=159.0,146.0,139.5,135.3,133.4,132.8,128.3,128.2,126.6,126 .3,125.7,122.0,122.0,121.6,53.3,49.0,32.5,31.8,26.4,22.7,14.1; HRMS(MALDI(N),100%)m / z calcd for C 58 H64 N2O4Zr: 942.3913, found: 942.3918.

[0089] TGA testing showed that the thermal decomposition temperature of the obtained derivative was greater than 340°C, indicating that it has good chemical stability.

[0090] Example 5

[0091] This embodiment provides a N,N'-di(2,6-diisopropylphenyl)-substituted bilateral silicon atom-fused fused ring aromatic imide derivative, and its synthesis route is as follows:

[0092]

[0093] The specific synthesis steps are as follows:

[0094] (1) Add 520 mg of dibromo-substituted silicon-fused biphenyl, 69 mg of tetrakistriphenylphosphine palladium and 411 mg of potassium carbonate to a reaction bottle containing 500 mg of diboron ester-substituted N,N'-2,6-diisopropylphenyl-naphthalene diimide;

[0095] (2) Under nitrogen protection, inject 10 ml of tetrahydrofuran and 2 ml of water into the mixture prepared in step (1), and stir at 80° C.;

[0096] (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 251 mg of a blue-purple powder of N,N'-di(2,6-diisopropylphenyl)-substituted bilaterally silicon-fused fused ring aromatic imide derivative with a yield of 40%.

[0097] The structure was confirmed by NMR and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 8.22 (d, 4H), 7.78 (d, 4H), 7.50 (t, 2H) ,7.38(d,4H),7.25(t,4H),3.28-3.23(m,4H),1.36(d,24H),1.06(t,20H); 13 C NMR (100MHz, CD2Cl2, 298K): δ=158.6,142.7,141.3,136.3,134.3,133.6,131.8,129.6,1 28.2,126.9,126.2,125.3,123.5,121.6,28.4,23.3,12.3,6.9; HRMS(MALDI(N),100%)m / z calcd for C 70 H66 N2O4Si2: 1054.4561, found: 1054.4568.

[0098] TGA testing shows that its thermal decomposition temperature is greater than 346°C, indicating that it has good chemical stability.

[0099] Example 6

[0100] This embodiment provides an N,N'-di(n-octyl)-substituted bilateral tin atom-fused fused ring aromatic imide derivative, and its synthesis route is as follows:

[0101]

[0102] The specific synthesis steps are as follows:

[0103] (1) To a reaction bottle containing 500 mg of bis-boronic acid-substituted N,N'-di(n-octyl)-substituted-naphthalene diimide, 873 mg of dibromo-substituted tin-fused biphenyl, 61 mg of bis(triphenylphosphine)palladium dichloride and 458 mg of sodium carbonate were added;

[0104] (2) Under nitrogen protection, inject 10 ml of toluene and 2 ml of water into the mixture prepared in step (1), and stir at 110° C.;

[0105] (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 423 mg of a blue-purple powder of a bilaterally tin-fused condensed aromatic imide derivative substituted with N,N'-di(n-octyl) atoms, with a yield of 45%.

[0106] The structure was confirmed by NMR and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 8.26 (d, 4H), 7.78 (d, 4H), 7.26 (t, 4H) ,3.16(t,4H),1.66(m,4H),1.28-1.26(t,20H),0.90(t,6H),0.46(s,12H); 13 C NMR (100MHz, CD2Cl2, 298K): δ=159.3,142.7,134.3,128.3,128.2,126.6,126.3,125.3,125.3,122 .0,122.0,121.6,121.6,40.2,31.9,30.2,29.3,29.3,26.7,22.7,14.1; HRMS(MALDI(N),100%)m / z calcd for C 58 H58 N2O4Sn2: 1086.2443, found: 1086.2448.

[0107] TGA testing shows that its thermal decomposition temperature is greater than 340°C, indicating that it has good chemical stability.

[0108] Example 7

[0109] This embodiment provides a N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted bilaterally germanium atom-fused fused-ring aromatic imide derivative, and its synthesis route is as follows:

[0110]

[0111] The specific synthesis steps are as follows:

[0112] (1) Add 402 mg of dibromo-substituted germanium-fused biphenyl, 48 mg of tetrakistriphenylphosphine palladium and 16 mg of cuprous iodide to a reaction bottle containing 500 mg of ditin-substituted N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted naphthalene diimide;

[0113] (2) Under nitrogen protection, inject 10 ml of toluene into the mixture prepared in step (1) and stir at 110° C.;

[0114] (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 231 mg of a blue-purple powder of N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted bilaterally germanium atom-fused condensed aromatic imide derivative with a yield of 47%.

[0115] The structure was confirmed by NMR and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 8.24 (d, 4H), 7.73 (d, 4H), 7.26 (t, 4H), 3.56 (t, 4H), 1.51 (m, 8H), 1.02 (t, 12H); 13 CNMR (100MHz, CD2Cl2, 298K): δ=159.3,142.7,134.3,128.3,128.2,126.6,126.3,125.3,125.3,122 .0,122.0,121.6,121.6,120.2,118.2,103.1,40.0,40.0,22.0,22.0,7.6; HRMS(MALDI(N),100%)m / z calcd for C 54H 36 F 14 Ge2N2O4: 1190.0872, found: 1190.0877.

[0116] TGA testing shows that its thermal decomposition temperature is greater than 348°C, indicating that it has good chemical stability.

[0117] Example 8

[0118] This embodiment provides an N,N'-di(1-pentylhexyl)-substituted bilateral zirconium atom-fused fused ring aromatic imide derivative, and its synthesis route is as follows:

[0119]

[0120] The specific synthesis steps are as follows:

[0121] (1) Add 503 mg of dibromo-substituted zirconium-fused biphenyl, 50 mg of tetrakistriphenylphosphine palladium and 16 mg of cuprous iodide to a reaction bottle containing 500 mg of ditin-substituted N,N'-di(1-pentylhexyl)-substituted naphthalene diimide;

[0122] (2) Under nitrogen protection, inject 10 ml of toluene into the mixture prepared in step (1) and stir at 115° C.;

[0123] (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 244 mg of a blue-purple powder of N,N'-di(1-pentylhexyl)-substituted bilateral zirconium atom-fused condensed ring aromatic imide derivative with a yield of 43%.

[0124] The structure was confirmed by NMR and high-resolution mass spectrometry. 1 H NMR (400MHz, CD2Cl2, 298K, ppm): δ = 8.26 (d, 4H), 7.76 (d, 4H), 7.26 (t, 4H), 6.52-6.4 1(m,16H),3.52(m,2H),2.93(t,4H),1.51(m,8H),1.29-1.27(m,24H),0.89(t,12H); 13C NMR (100MHz, CD2Cl2, 298K): δ=159.0,142.7,134.3,132.8,128.3,128.2,126.6,126.4,126.3,125.7,125.3 ,122.0,122.0,121.6,121.6,53.2,50.0,49.9,32.5,32.5,31.8,26.4,22.7,14.1; HRMS(MALDI(N),100%)m / z calcd for C 80 H 78 N2O4Zr2: 1310.4052, found: 1310.4048.

[0125] TGA testing shows that its thermal decomposition temperature is greater than 340°C, indicating that it has good chemical stability.

[0126] Experimental Example 1

[0127] This experimental example detects the application of the heteroatom-fused fused-ring aromatic imide derivatives described in the method of the present invention as organic semiconductor n-type electron transport materials in organic field effect transistors.

[0128] The N,N'-di(2,2,3,3,4,4,4-heptafluorobutyl)-substituted unilateral and bilateral germanium atom-fused fused-ring aromatic imide derivatives obtained in Examples 3 and 7 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 50nm gold electrodes (evaporation method), the gate electrode was a gallium-indium composite, and the insulating layer was an OTS-modified SiO2 / Si substrate. The organic semiconductor layer was spin-coated, and the thickness of the prepared film was 40-60nm; and it was heated and annealed at 200°C, the solvent was chloroform, and the concentration was 1mg / ml. All tests were carried out in air, and the field effect mobility test results of the two materials are shown in Table 1 below:

[0129] Table 1 - Field effect mobility test results of two materials

[0130]

[0131]

[0132] Electron mobility μ e Indicates the migration ability of electrons in semiconductors under different electric fields. e max It indicates the maximum mobility of electrons in a semiconductor. on / I offV 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.

[0133] 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 type of material has very good electron transmission ability in the air and has the potential to be used as an electron acceptor material in organic optoelectronic devices.

[0134] Experimental Example 2

[0135] This experimental example tests the application of the heteroatom-fused fused-ring aromatic imide derivatives of the present invention as organic semiconductor n-type electron transport materials in organic solar cells.

[0136] The N,N'-di(1-pentylhexyl)-substituted unilateral and bilateral zirconium atom-fused condensed ring aromatic imide derivatives obtained in Examples 4 and 8 were used as acceptor materials for organic solar cells, and PBDB-T was used as a donor material for the organic photoelectric layer to construct a bulk heterojunction organic solar device structure. The inverted device structure was ITO / ZnO(30nm) / BHJ / MoOx(10nm) / Al, wherein ZnO and MoOx were used as electron transfer electrodes and hole transfer electrodes, respectively. The solar cell device parameters are shown in Table 2 below. The solvent used was o-xylene, and the light source was AM 1.5G (100mW cm -2 ), the additive is CN (1-chloronaphthalene).

[0137] Table 2 - Solar cell device parameters

[0138]

[0139] 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 OCThere 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.

[0140] It can be seen from Table 2 that the heteroatom-fused fused-ring aromatic imide derivative material of the present invention, as an acceptor material for an organic solar cell, 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 heteroatom-fused fused-ring aromatic imide derivative of the present invention has a very high photocurrent density Jsc, and has a matching energy level and good film-forming property with common donor materials, and obtains a higher open circuit voltage V OC and fill factor FF, achieving high photoelectric conversion efficiency, thus providing new materials for the development of light and flexible organic solar cells.

[0141] 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 heteroatom-fused fused-ring aromatic imide derivative, 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 are the same or different; M is selected from any one of the following four heteroatoms: Si, Ge, Sn or Zr, and M is the same or different; R2 is selected from any of the following groups: each independently represents hydrogen, a group containing a substituent or a group without 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 an alkyleneoxy heterocyclic group, a cyclopentadienyl group, a cyclopentadienyl group or a 2,2'-biphenyl group, wherein R2 are the same or different.

2. The heteroatom-fused fused-ring aromatic imide derivative 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; 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.

3. The heteroatom-fused fused-ring aromatic imide derivative 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.

4. The heteroatom-fused fused-ring aromatic imide derivative 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; 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.

5. The heteroatom-fused fused-ring aromatic imide derivative 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. The heterocyclic group is selected from any one or a combination of the following groups: thienyl, furanyl, pyranyl, phenoxathiyl, pyrrolyl, imidazolyl, pyrazolyl, pyridinyl, 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, benzo Thiazolyl, benzothienyl, 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, or a group derived from the ring of the above groups fused with the ring of the aryl group.

6. The heteroatom-fused fused-ring aromatic imide derivative according to claim 1, characterized in that: The R1 is selected from any one or a combination of the following groups: each independently represents hydrogen, C with or without a substituent; 1-60 Alkyl, C 1-60 Alkoxy, C 5-60 Aryl or C 3-60 One or a combination of cycloalkyl; The R2 is selected from any one or a combination of the following groups: each independently represents hydrogen, an alkyl group, an alkoxy group, an aryl group, a cyclopentadienyl group, a biphenyl group, or a substituted or unsubstituted group, preferably C 1-60 Alkyl, C 1-60 Alkoxy, C 5-60 Aryl, C 3-60 Cycloalkyl, cyclopentadienyl, cyclopentadienyl, 2,2'-biphenyl.

7. The heteroatom-fused fused-ring aromatic imide derivative 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 heteroatom-fused fused-ring aromatic imide derivative according to any one of claims 1 to 7 in any of the following: (1) Application as light absorbing material or electron transport material in organic field effect transistors, organic electroluminescent devices, organic thermochromic elements or organic solar cells; (2) Application as intermediates in the preparation of novel condensed-ring aromatic imide derivative electron acceptor materials.

9. The method for preparing the heteroatom-fused fused-ring aromatic imide derivative according to any one of claims 1 to 7, characterized in that: The steps include: 1) placing mono-boric acid ester substituted or di-boric acid ester substituted 1,4:5,8-naphthalene diimide represented by formula (a1), mono-boric acid substituted or di-boric acid substituted 1,4:5,8-naphthalene diimide represented by formula (a2), or mono-tin substituted or di-tin substituted 1,4:5,8-naphthalene diimide represented by formula (a3) ​​into a reactor; 2) Under nitrogen or argon protection, add any compound represented by formula (b) into the reactor in step 1), then add palladium catalyst, ligand, base and organic solvent, and stir and heat the solution to 50-130° C.; 3) reacting for 5 to 24 hours, and obtaining the heteroatom-fused fused-ring aromatic imide derivative through post-treatment; Among them, R2 in formula (a3) ​​and formula (b) is the same as R2 in claim 1; R1 in formula (a1), (a2) and (a3) ​​is the same as R1 in claim 1.

10. The preparation method according to claim 9, characterized in that: Taking the compound represented by formula (a) as 1 equivalent, the equivalent ratio of the palladium catalyst is 0.01 to 4, preferably 1 to 3; the equivalent ratio of the ligand is 0.01 to 20, preferably 0.01 to 10; the equivalent ratio of the base is 2 to 15, preferably 2 to 12; the equivalent ratio of the compound represented by formula (b) is 1 to 5, preferably 1 to 3.

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