JPH04342584A - Thia and/or selena-fluvalene group-containing compound - Google Patents

Abstract

PURPOSE:To provide the subject novel compound having a good electron- donating property, capable of directly forming a complex with an electron acceptor, and having excellent thermal stability. CONSTITUTION:A compound of the formula [X1a-X4a and X1b-X4b are S, Se; Y is multicyclic aromatic group comprising two or more benzene rings condensed with each other, hetero atom-containing aromatic five-membered ring; Z1a, Z2a, Z1b, Z2b are H, CnH2n+1]. For example, 2,6-bis[2-(tetrathiafluvalen-2-yl) vinyl)-naphthalene. The compound of the formula is produced by reacting 1 mole of formyltetrathiafluvalene, etc., with 0.5 mole of a condensed multi-cyclic aromatic compound phosphonic acid such as a naphthalene phosphonic acid ester in the presence of 1 mole of a base such as lithium ethoxide in an ether solvent at room temperature for several minutes to 10 hours.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a novel compound containing a thia and/or selenafulvalenyl group and a conductive complex using this novel compound as an electron donor. (ii) it is possible to obtain a conductive complex by simply mixing it directly with an electron acceptor;
The present invention relates to a novel compound containing thia and/or selenafulvalenyl groups, which has advantages such as excellent thermal stability, and a conductive complex using this novel compound as an electron donor.

0002

2. Description of the Related Art Organic compounds are generally considered to be insulators, but active research is being conducted to find organic compounds that have electrical conductivity. As organic conductive compounds,
Charge transfer complexes are known in which an electron donor and an electron acceptor are bonded by a charge transfer force between them. Among such charge transfer complexes, compounds having a thiafulvalene skeleton such as tetrathiafulvalene (TTF), tetramethyltetrathiafulvalene (TMTTF), and bisethylenedithiotetrathiafulvalene (BEDTTTF) are particularly used as electron donors. It has been revealed that complexes obtained by reacting various electron acceptors with this complex exhibit relatively good conductivity [Kagaku Review Vol. 42, p. 59 (19
1983)].

0003

[Problems to be Solved by the Invention] However, among the above-mentioned electron-donating compounds having a thiafulvalene skeleton, TTF has a low melting point of 115 to 119°C and poor thermal stability, so it cannot be applied to parts exposed to high temperatures. The disadvantage is that the range of use is limited. Also TMT
TF and BEDTTTF etc. have T in terms of thermal stability.
Although it is superior to TF, it does not have sufficient electron donating properties and does not form complexes with commonly used electron acceptors just by mixing them directly, and requires complicated methods such as electrolytic crystallization to form complexes. There is a drawback that it must be done. As described above, no organic compound has been found to date that has good electron donating properties, can be directly complexed with an electron acceptor, and has excellent thermal stability.

[0004] Therefore, the first object of the present invention is to provide a novel organic compound that has good electron donating properties, can be directly complexed with an electron acceptor, and has excellent thermal stability. It is in. The second object of the present invention is to develop electrical conductivity using a novel organic compound as an electron donor, which has good electron donating properties, can be directly complexed with an electron acceptor, and has excellent thermal stability. The objective is to provide complexes.

[0005]

[Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have found that (1) a compound having specific thia and/or selenafulvalenyl groups at both ends; An organic compound represented by the following general formula (I) in which these are linked with a specific aromatic divinyl group has good electron donating properties and can be directly complexed with an electron acceptor,
and (2) an electron donor obtained by using the organic compound represented by the general formula (I) as an electron donor and reacting the electron donor with an electron acceptor. It was discovered that a complex consisting of a predetermined molar ratio of electron acceptor and electron acceptor has electrical conductivity, and the present invention was completed based on these findings.

That is, the present invention provides general formula (I)

00
07]

[Chemical 2]

[In the formula, X1a, X2a, X3a, X4a
, X1b, X2b, X3b and X4b are each independently S or Se, Y is a polycyclic aromatic group in which two or more benzene rings are condensed or a hetero atom-containing aromatic 5-membered ring group, Z2a, Z1b and Z2b each independently represent a hydrogen atom, Cn H2n+1 (n=an integer of 1 to 5), XCn H2n+1 (X=S or Se, n=1 to
an integer of 5) or Z1a and Z2a and Z1
Cn H2n (n = integer of 1 to 5) or X (Cn H2n) m X (X = S or Se
, m = an integer of 1 to 3), and R1a, R2a, R3a
, R1b, R2b and R3b are each independently a hydrogen atom or CnH2n+1 (n = an integer of 1 to 5)]
The gist is a thia and/or selenafulvalenyl group-containing compound represented by:

The present invention also provides an electron donor obtained by using the thia and/or selenafulvalenyl group-containing compound of the general formula (I) as an electron donor and reacting this electron donor with an electron acceptor. / electron acceptor molar ratio is 1/0.
The gist is a conductive complex having a conductivity of 1 to 1/10.

The present invention will be explained in detail below. As is clear from the above general formula (I), the novel compound containing thia and/or selenafulvalenyl groups of the present invention has general formula (II) at both ends thereof.

[0011]

[C3]

and general formula (III)

[0013]

[C4]

It has a thia and/or selenafulvalenyl group as shown below. In general formula (II) and general formula (III), X1a, X2a, X3a
, X4a, X1b, X2b, X3b and X4b are each independently S or Se. Therefore, specific examples of general formula (II) and general formula (III) include, but are not limited to, the following.

[0015]

[C5]

[0016]

[C6]

Also, the above formula groups (II) and (III)
, Z1a, Z2a, Z1b, and Z2b each independently represent a hydrogen atom, a lower alkyl group represented by the formula Cn H2n+1 (n = an integer from 1 to 5), and a formula XCn H2n
+1 (X=S or Se, n=an integer of 1 to 5) is a thio or seleno lower alkoxy group. The lower alkyl group represented by the formula Cn H2n+1 herein includes methyl group, ethyl group, n-propyl group, i
so-propyl group, n-butyl group, iso-butyl group,
Examples include tert-butyl group. Also, the formula XCn
The thio or seleno lower alkoxy group represented by H2n+1 includes thiomethoxy group, selenomethoxy group, thioethoxy group, selenoethoxy group, thio-n-propoxy group, seleno-n-propoxy group, thio-iso-
propoxy group, seleno-iso-propoxy group, thio-
n-butoxy group, seleno-n-butoxy group, thio-is
o-butoxy group, seleno-iso-butoxy group, thio-
Examples include tert-butoxy group and seleno-tert-butoxy group.

Also, the above formula groups (II) and (III)
In, Z1a and Z2a and Z1b and Z2b are
These are connected to form an alkylene group represented by the formula Cn H2n (n = an integer of 1 to 5) or the formula X(CH2)m
An alkylene group having a sulfur and/or selenium atom at the terminal, such as a dithioalkylene group or a diselenoalkylene group, represented by X (X=S or Se, m=an integer of 1 to 5) may be constituted. Representative examples of the alkylene group represented by the formula Cn H2n herein include methylene, ethylene, propylene, and butylene groups. Also, the formula X(CH2)m
Representative examples of the alkylene group represented by X having a sulfur and/or selenium atom at the end include S-CH2
-S, Se-CH2 -Se, S-(CH2)2
-S, Se-(CH2)2-Se, and the like. In addition, in the above formula groups (II) and (III), R1a and R1b are each independently a hydrogen atom or a Cn
H2n+1 (n=an integer from 1 to 5). Cn here
Examples of the lower alkyl group represented by H2n+1 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, and tert-butyl group.

The compound of the present invention represented by the general formula (I) has thia and/or selenafulvalenyl groups represented by the above general formulas (II) and (III) at both ends, and these are Formula (IV) -CR2a=CR3a-Y-CR3b=CR2b-
It is formed by linking with an aromatic divinyl group represented by (IV). R2a, R in this general formula (IV)
3a, R2b and R3b are each independently a hydrogen atom or Cn H2n+1 (n=an integer of 1 to 5), and have the formula C
Representative examples of the lower alkyl group represented by n H2n+1 include methyl group, ethyl group, n-propyl group, iso-
propyl group, n-butyl group, iso-butyl group, ter
Examples include t-butyl group.

Further, Y is a polycyclic aromatic group having two or more condensed benzene rings or a hetero atom-containing aromatic five-membered ring group. Typical examples of the polycyclic aromatic group as Y include groups such as naphthalene group, anthracene group, phenanthrene group, tetracene group, pyrene group, perylene group, and groups such as alkyl group, alkoxy group, aryloxy group, Examples include groups substituted with 1 to 6 at least one selected from acyl groups, alkoxycarbonyl groups, and halogen atoms. Here, typical examples of substituted alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-
Examples include butyl group. Further, typical examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and the like. A typical example of the aryloxy group includes a phenoxy group. Representative examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, and benzoyl group. Representative examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, and butoxycarbonyl group. Furthermore, typical examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

On the other hand, the hetero atom-containing aromatic 5-membered ring group as Y in the general formula (IV) is, for example, represented by the following formula:

[0022]

[C7]

[In the formula, X5 and X6 are each independently O, S, Se or NR6 (R6 is a hydrogen atom, an alkyl group or an acyl group), and R4 and R
5 is each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a phenyl group, or a halogen atom] is preferred.

Representative examples of the alkyl group as R4 and R5 in the above formula representing a hetero atom-containing aromatic five-membered ring group include methyl group, ethyl group, n-propyl group, i
so-propyl group, n-butyl group, iso-butyl group,
Examples include tert-butyl group. Further, typical examples of alkoxy groups include methoxy group, ethoxy group, propoxy group, butoxy group, iso-butoxy group, tert-
Examples include butoxy group. A typical example of the aryloxy group includes a phenoxy group. Representative examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, iso-butyryl group, and benzoyl group. Representative examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, and the like. Representative examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, typical examples of the alkyl group as R6 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-
Typical examples of acyl groups include butyl groups, etc.
Examples include formyl group, acetyl group, propionyl group, butyryl group, iso-butyryl group, and benzoyl group.

The compound of the present invention represented by the general formula (I) can be produced, for example, by the known Wittig reaction. In one preferred example of this production method, 1 mole of a formylthia and/or selenafulvalene compound such as formyltetrathiafulvalene or formyltetraselenafulvalene and a naphthalene phosphonic acid ester are mixed in an ether-based or alcohol-based solvent. 0.5 mol of a phosphonic acid ester of a condensed polycyclic aromatic compound such as anthracene phosphonic acid ester and anthracene phosphonic acid ester are added in the presence of 1 mol of an appropriate base such as lithium ethoxide, n-butyllithium, or t-butoxypotassium. By reacting at room temperature for several minutes to about 10 hours, a desired compound in general formula (I) in which Y is a condensed polycyclic aromatic group can be obtained. If the reaction time is shorter than the above range, the yield will decrease, and even if the reaction is made longer than the above range, the yield will reach a plateau and no further improvement can be expected. In this reaction,
In place of the phosphonic acid ester of the condensed polycyclic aromatic compound, for example, by using a compound having triphenylphosphonium halide groups at both ends of the hetero atom-containing aromatic 5-membered ring group shown in Chemical Formula 7, the compound of the general formula (I ), wherein Y is a 5-membered heteroatom-containing aromatic group.

The following are representative examples of the compounds of the present invention represented by the general formula (I). Compound 1 2,6-bis[2-(tetrathiafulvalen-2-yl)vinyl]-naphthalene compound 2 9,10-bis[2-(tetrathiafulvalen-2-yl)vinyl]-anthracene compound 3 2, 6-bis[2-(tetraselenafulvalen-2-yl)vinyl]-naphthalene compound 4 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-thiophene compound 5 2,5-bis [2-(tetraselenafulvalen-2-yl)vinyl]-thiophene compound 6 2,6-bis[2-(6,7-ethylenedithiotetrathiafulvalen-2-yl)vinyl]-naphthalene compound 7 2, 6-bis[2-(6,7-methylene dithiotetrathiafulvalen-2-yl)vinyl]-naphthalene compound 8 2,6-bis[2-(1,4-dithia-5,8-diselenafulvalene) -2-yl)vinyl]-naphthalene compound 9 2,6-bis[2-(1,4-diselena-5,8-dithiafulvalen-2-yl)vinyl]-naphthalene compound 10 2,6-bis[ 2-(1-selena-4,5,8-trithiafulvalen-2-yl)vinyl]-naphthalene compound 11 2,6-bis[2-(6,7-dimethyltetrathiafulvalen-2-yl)vinyl ]-Naphthalene compound 12 2,6-bis[2-(6,7-dimethyltetraselenafulvalen-2-yl)vinyl]-naphthalene compound 13 1,4-bis[2-(tetrathiafulvalen-2-yl) ) vinyl]-naphthalene compound 14 1,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-naphthalene compound 15 2,6-bis[2-(tetrathiafulvalen-2-yl)vinyl]- 1,5-dimethylnaphthalene compound 16 2,6-bis[2-(tetrathiafulvalen-2-yl)vinyl]-1,5-dichloronaphthalene compound 17 2,6-bis[2-(tetrathiafulvalen-2-yl)vinyl] 2-yl)vinyl]-1,4,5,8-tetramethylnaphthalene compound 18 9,10-bis[2-(tetraselenafulvalene-2-
yl)vinyl]-anthracene compound 19 1,4-bis[2-(tetrathiafulvalen-2-yl)vinyl]-anthracene compound 20 3,6-bis[2-(tetrathiafulvalen-2-yl)vinyl] -Phenanthrene compound 21 1,6-bis[2-(tetrathiafulvalen-2-yl)vinyl]-pyrene compound 22 2,5-bis[2-(6,7-ethylenedithiotetrathiafulvalen-2-yl) Vinyl]-thiophene compound 23 2,5-bis[2-(6,7-methylenedithiotetrathiafulvalen-2-yl)vinyl]-thiophene compound 24 2,5-bis[2-(1,4-dithia- 5,8-diselenafulvalen-2-yl)vinyl]-thiophene compound 25 2,5-bis[2-(1,4-diselena-5,8-dithiafulvalen-2-yl)vinyl]-thiophene Compound 26 2,5-bis[2-(1-selena-4,5,8-trithiafulvalen-2-yl)vinyl]-thiophene Compound 27 2,5-bis[2-(6,7-dimethyltetra) Thiafulvalen-2-yl)vinyl]-thiophene compound 28 2,5-bis[2-(6,7-dimethyltetraselenafulvalen-2-yl)vinyl]-thiophene compound 29 2,5-bis[2- (Tetrathiafulvalen-2-yl)vinyl]-3-methylthiophene compound 30 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-3,4-dimethylthiophene compound 31 2,5- Bis[2-(tetrathiafulvalen-2-yl)vinyl]-3-phenylthiophene compound 32 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-3,4-diphenylthiophene compound 33 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-3,4-dichlorothiophene compound 34 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-3 ,4-dibromothiophene compound 35 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-3,4-dimethoxythiophene compound 36 2,5-bis[2-(tetrathiafulvalen-2-yl) yl)vinyl]-3,4-thiophenedicarboxylic acid dimethyl compound 37 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-furan compound 38 2,5-bis[2-(tetraselenaflu) Valen-2-yl)vinyl]-furan compound 39 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-pyrrole compound 40 2,5-bis[2-(tetraselenafulvalen-2) -yl)vinyl]-pyrrole compound 41 N-methyl-2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-pyrrole compound 42 N-acetyl-2,5-bis[2-(tetra Thiafulvalen-2-yl)vinyl]-pyrrole compound 43 N-benzoyl-2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-pyrrole compound 44 2,5-bis[2-(tetra thiafulvalen-2-yl)vinyl]-thieno[3,2-b]thiophene compound 4
5 2,5-bis[2-(tetraselenafulvalen-2-yl)vinyl]-thieno[3,2-b]thiophene compound 46 2,5-bis[2-(tetrathiafulvalen-2-yl) Vinyl]-3,6-dimethylthieno[3,2-b]thiophene compound 47 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-3,6-diphenylthieno[3,2- b]
Thiophene compound 48 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-seleno[3,2-b]selenophene compound 49 2,5-bis[2-(tetraselenafulvalen-2-yl) yl)vinyl]-seleno[3,2-b]selenophene compound 50 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-seleno[3,2-b]thiophene compound 5
1 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-thieno[3,2-b]furan

[0027]
The compound of the present invention represented by general formula (I) has electron donating properties and can form a conductive complex not only by ordinary electrochemical methods but also by direct mixing with an electron acceptor. be. The electron acceptor when forming the conductive complex may be either organic or inorganic.
Examples of organic electron acceptors include 7,7,8,8-tetracyanoquinodimethane, 2-methyl-7,7,8,8
-tetracyanoquinodimethane, 2,5-dimethyl-7,
7,8,8-tetracyanoquinodimethane, 2,5-diethyl-7,7,8,8-tetracyanoquinodimethane, 2
-Methoxy-7,7,8,8-tetracyanoquinodimethane, 2,5-dimethoxy-7,7,8,8-tetracyanoquinodimethane, 2-methoxy-5-ethoxy-7,7
, 8,8-tetracyanoquinodimethane, 2-methoxydihydrodioxabenzo-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane , 2-bromo-7,7,8,8-tetracyanoquinodimethane, 2,5-dibromo-7,7,8
, 8-tetracyanoquinodimethane, 2,5-diiodo-
7,7,8,8-tetracyanoquinodimethane, 2-chloro-5-methyl-7,7,8,8-tetracyanoquinodimethane, 2-bromo-5-methyl-7,7,8, 8-tetracyanoquinodimethane, 2-iodo-5-methyl-7
, 7,8,8-tetracyanoquinodimethane, 11,11
, 12,12-tetracyano-2,6-naphthoquinodimethane, 1,1,2,3,4,4-hexacyanobutadiene, sodium-13,13,14,14-tetracyanodiphenoxydimethane, tetracyano ethylene, o-
Examples include benzoquinone, p-benzoquinone, 2,6-naphthoquinone, diphenoquinone, tetracyanodiquinone, p-fluoranyl, and tetrachlorodiphenoquinone. In addition, examples of inorganic electron acceptors include iodine,
Halogen elements such as bromine and chlorine, I3, I2 Br,
Trihalide anions such as IBr2, Br3, Cl3, SCN, Cu(SCN)2, AuI2, A
Pseudohalogen molecules such as uBr2, AuCl2, Cl
Examples include electron-accepting molecules such as O4, PF6, and BF4.

In this charge transfer complex, the electron donor (
The molar ratio (D/A) of the compound of the present invention of general formula (I) and the electron acceptor is 1/0.1 to 1/10. The reason is that when D/A exceeds 1/0.1, the conductivity decreases, while when D/A is less than 1/10, the conductivity similarly deteriorates.

The obtained complex has electrical conductivity and can be used as an organic electrically conductive material. Also, general formula (I)
The compound of the present invention represented by has better thermal stability than the existing tetrathiafulvalene (TTF), and therefore the field of application and use of this compound and the complex obtained by the reaction of this compound with an electron acceptor are The range can be expanded. For example, a complex containing the compound of the present invention represented by general formula (I) as an electron donor can be used for printed wiring of cars exposed to high temperatures.

[0030]

[Examples] The present invention will be explained in more detail with reference to Examples below. [Production example of the compound of the present invention of general formula (I)] Example 1
Preparation of 2,6-bis[2-(tetrathiafulvalen-2-yl)vinyl]-naphthalene (compound 1) 2,6-
Bis(bromomethyl)naphthalene 5g (15.9mmo
1) and 30 g of triphenylphosphine were placed in 100 ml of dimethylformamide (hereinafter referred to as DMF) and heated in an oil bath (bath temperature of about 130° C.). After 50 minutes, it was filtered while still hot, washed with acentone, and dried to give 8.5 g of naphthalene phosphonic acid ester (yield 93%).
) was obtained. The melting point of this material was 144.5-146°C. 2 g (3.47 mmol) of this substance was suspended in 30 ml of tetrahydrofuran (hereinafter referred to as THF), and 3.5 ml of an n-hexane solution of n-butyllithium (n-butyllithium concentration 14% by weight) was added to the
It was dripped over several minutes. Furthermore, a solution of 1.6 g (2 equivalents) of 2-formyltetrathiafulvalene dissolved in 10 ml of THF was added dropwise, and the mixture was stirred at room temperature for 6 hours to carry out a reaction. After that, several ml of methanol was added dropwise to terminate the reaction, followed by evaporation, washing with water and methanol sequentially, filtering and drying, and 0.5 g of the target substance (
A yield of 25% was obtained. It was confirmed from the mass spectrometry results (M/Z) and elemental analysis results shown in Table 1 that the finally obtained substance was the target substance represented by the following formula.

[0031]

[Chemical formula 8]

The thermal decomposition temperature Td of the target substance obtained in this way is 235°C (thermal decomposition temperature is TG (thermogravimetric analysis)
(defined as the temperature at which the weight decreases by 5 wt%), and it was confirmed that the temperature was excellent in thermal stability. In addition, the following conditions reference electrode Ag/AgCl supporting electrolyte
n-Bu4 NBF4 solvent
Chlorobenzene electrolyte concentration 10
0mmol/l Sample compound concentration 0.5mmol
The first value determined by cyclic voltammetry at /l
It can be seen that the oxidation potential E1 is as low as 0.52V, indicating that it has excellent electron donating properties.

Example 2 Preparation of 9,10-bis[2-(tetrathiafulvalen-2-yl)vinyl]-anthracene (compound 2) 9,10-bis(chloromethyl)anthracene 5 g (1
8.2 mmol) and 30 g of triphenylphosphine in 100 ml of DMF, and put them in an oil bath (bath temperature approx.
30°C). After 30 minutes, the mixture was filtered while still hot, washed with acentone, and dried to obtain 9 g (yield: 92%) of anthracenephosphonic acid ester. The melting point of this material was 160-161.5°C. 2g of this substance (
3.7 mmol) was suspended in 30 ml of THF, and 4 ml of a solution of n-butyllithium in n-hexane (n-butyllithium concentration: 14% by weight) was added dropwise over 5 minutes under an argon stream. Furthermore, a solution of 1.7 g (2 equivalents) of 2-formyltetrathiafulvalene dissolved in 10 ml of THF was added dropwise, and the mixture was stirred at room temperature for 2 hours to carry out a reaction. After that, several ml of methanol was added dropwise to terminate the reaction, followed by evaporation, washing with water and methanol in sequence, filtration, drying, and recrystallization from DMF. %) was obtained. It was confirmed from the mass spectrometry results (M/Z) and elemental analysis results shown in Table 1 that the finally obtained substance was the target substance represented by the following formula.

[0034]

[Chemical formula 9]

The thermal decomposition temperature Td of the target substance thus obtained was 260°C, and it was confirmed that it had excellent thermal stability. In addition, the first
It can be seen that the oxidation potential E1 is as low as 0.60V, indicating that it has excellent electron donating properties.

Example 3 2,6-bis[2-(tetraselenafulvalen-2-yl)vinyl]-naphthalene (
Preparation of compound 3) Naphthalene phosphonic acid ester 2 g (3.5 mmol
) was suspended in 30 ml of THF and dried under an argon stream.
3.5 ml of an n-hexane solution of -butyllithium (n-butyllithium concentration: 14% by weight) was added dropwise over 5 minutes. Furthermore, 2-formyltetraselenafulvalene 2.9
A solution of g (2 equivalents) dissolved in 10 ml of THF was added dropwise, and the mixture was stirred at room temperature for 2 hours to carry out a reaction. after that,
After terminating the reaction by dropping several ml of methanol, it was evaporated, washed with water and methanol sequentially, filtered, dried, and then recrystallized from DMF to obtain 0.8 mL of the target substance.
g (yield 24%) was obtained. It was confirmed from the mass spectrometry results (M/Z) and elemental analysis results shown in Table 1 that the finally obtained substance was the target substance represented by the following formula.

[0037]

[Chemical formula 10]

The thermal decomposition temperature Td of the target substance thus obtained was 230°C, and it was confirmed that it had excellent thermal stability. In addition, the first
It can be seen that the oxidation potential E1 is as low as 0.65V, indicating that it has excellent electron donating properties.

Example 4 Preparation of 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-thiophene (compound 4) 2,5-bis(chloromethyl)thiophene 9.1 g (5
0.0 mmol) and triphenylphosphine 28.9
g (110 mmol) was dissolved in 200 ml of DMF, heated to 130°C, and reacted for 2 hours. The resulting white solid was filtered hot, washed with DMF and methylene chloride, and dried to give 33.8 g (48.0 g) of 2,5-bis(triphenylphosphoniomethyl)thiophene dichloride.
mmol, yield 96%). 0.71g of this substance
(1.0 mmol) and 0.46 g (2.0 mmol) of 2-formyltetrathiafulvalene were suspended in 50 ml of absolute ethanol. In this, 1.5ml of 1.6M n-butyllithium/n-hexane solution (2.4mmol
A lithium ethoxide solution prepared from 1) and 30 ml of absolute ethanol was added dropwise at room temperature over 30 minutes, and after the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes to carry out the reaction. Thereafter, 10 ml of water was added to terminate the reaction, and the resulting solid was filtered and washed with methanol, and this was recrystallized from DMF to form shiny red plate-like crystals of the desired substance.
0 g (yield 55%) was obtained. It was confirmed from the mass spectrometry results (M/Z) and elemental analysis results shown in Table 1 that the finally obtained substance was the target substance represented by the following formula.

[0040]

[Chemical formula 11]

The thermal decomposition temperature Td of the target substance thus obtained was 260°C, and it was confirmed that it had excellent thermal stability. In addition, the first
It can be seen that the oxidation potential E1 is as low as 0.40V, indicating that it has excellent electron donating properties.

Example 5 2,5-bis[2-(tetraselenafulvalen-2-yl)vinyl]-thiophene (
Preparation of compound 5) 0.71 g (1.0 mmol) of 2,5-bis(triphenylphosphoniomethyl)thiophene dichloride and 2-
Formyltetraselenafulvalene 0.46g (2.0m
mol) was suspended in 50 ml of absolute ethanol. A lithium ethoxide solution prepared from 1.5 ml (2.4 mmol) of a 1.6 M n-butyllithium/n-hexane solution and 30 ml of absolute ethanol was added dropwise to this solution over a period of 30 minutes at room temperature. The reaction was carried out by stirring at room temperature for 30 minutes. Thereafter, 10 ml of water was added to terminate the reaction, and the resulting solid was filtered and washed with methanol, and this was recrystallized from DMF to give 0.43 g of the desired substance as shiny red plate-shaped crystals (yield: 45 %) was obtained. It was confirmed from the mass spectrometry results (M/Z) and elemental analysis results shown in Table 1 that the finally obtained substance was the target substance represented by the following formula.

[0043]

[Chemical formula 12]

The thermal decomposition temperature Td of the target substance thus obtained was 240°C, and it was confirmed that it had excellent thermal stability. In addition, the first
It can be seen that the oxidation potential E1 is as low as 0.45V, indicating that it has excellent electron donating properties.

[0045]

[Table 1]

[Production Example of Complex] Example 6 10 mg of 2,6-bis[2-(tetrathiafulvalen-2-yl)vinyl]-naphthalene (compound 1) obtained in Example 1 was placed in a flask. 50 ml of benzonitrile was added to this and heated to 120°C to dissolve it. 100 mg of tetra-n-butylammonium triiodide (hereinafter abbreviated as n-Bu4 NI3) was mixed with this,
Stirred for 10 minutes. After slowly cooling to room temperature, the generated reaction product was filtered, washed with dichloromethane, and dried to obtain a complex having Compound 1 as an electron donor and I3 as an electron acceptor. Incidentally, whether or not the finally obtained substance was a complex was determined based on whether or not the electrical conductivity measured as described below was high.・Measurement of electrical conductivity Put about 2 mg of sample into a glass cell with an inner diameter of 1 mm, pressurize it with a cylinder pressure of about 130 kg/cm2, and cut it into a glass cell with a length of about 1 mm.
A sample for measuring electrical conductivity was formed into a columnar shape of 3 mm and 1 mm in diameter, and electrodes were attached to this sample using gold paste to measure the electrical conductivity using the four-terminal method.

The electrical conductivity of the sample thus measured was as high as 100 S/cm, and it was determined that it was a complex. In addition, the molar ratio D/A (however, average value) of electron donor/electron acceptor in the complex obtained in Example 6 is expressed by the following formula d:
Molecular weight of the electron donor a: Molecular weight of the electron acceptor w: Weight ratio of the measured atoms (%) r: The ratio of the measured atoms in the electron acceptor was determined to be 1/1.3.

Example 7 10 mg of 9,10-bis[2-(tetrathiafulvalen-2-yl)vinyl]-anthracene (compound 2) obtained in Example 2 was placed in a flask, and 50 ml of benzonitrile was added thereto. In addition, it was heated to 120°C to dissolve it. To this, 100 m of tetra-n-butylammonium monobromodiodide (abbreviated as n-Bu4 NI2 Br) was added.
g and stirred for 10 minutes. After slowly cooling to room temperature,
The generated reaction product was filtered, washed with dichloromethane, and then dried to obtain a complex having Compound 2 as an electron donor and I2Br as an electron acceptor. The electrical conductivity complex of the finally obtained substance was measured in the same manner as in Example 6. The electrical conductivity was as high as 5 S/cm at room temperature, and this substance was judged to be a complex. Further, the molar ratio D/A of electron donor/electron acceptor in the complex obtained in Example 7 was determined in the same manner as in Example 6, and was found to be 1/1.2.

Example 8 In place of Compound 1 in Example 6, 2,6-bis[2-(tetraselenafulvalene-2-
A complex having Compound 3 as an electron donor and I3 as an electron acceptor was obtained in the same manner as in Example 6 except that 10 mg of Compound 3 was used. The electrical conductivity complex of the finally obtained substance was measured in the same manner as in Example 6, and it was as high as 200 S/cm at room temperature, and this substance was judged to be a complex. Further, the molar ratio D/A of electron donor/electron acceptor in the complex obtained in Example 8 was determined in the same manner as in Example 6, and was found to be 1/1.2.

Example 9 10 mg of 2,5-bis[2-(tetrathiafulvalen-2-yl)vinyl]-thiophene (compound 4) obtained in Example 4 was placed in a flask, and 20 ml of benzonitrile was added to it. In addition, it was heated to 120°C to dissolve it. 100 mg of n-Bu4 NI3 was mixed with this and stirred for 1 minute. After slowly cooling to room temperature, the generated reaction product was filtered, washed with dichloromethane, and dried to obtain a complex having Compound 4 as an electron donor and I3 as an electron acceptor. The electrical conductivity complex of the finally obtained substance was measured in the same manner as in Example 6, and it was as high as 300 S/cm at room temperature, and this substance was judged to be a complex. Furthermore, when the molar ratio D/A of electron donor/electron acceptor in the complex obtained in Example 9 was determined in the same manner as in Example 6, it was found to be 1/1.
It was 3.

Example 10 In place of compound 4 in Example 9, 2,5-bis[2-(tetraselenafulvalene-2-
A complex using Compound 5 as an electron donor and I3 as an electron acceptor was obtained in the same manner as in Example 9 except that 10 mg of Compound 5 was used. The electrical conductivity complex of the finally obtained substance was measured in the same manner as in Example 9, and was as high as 800 S/cm at room temperature, and this substance was judged to be a complex. In addition, the molar ratio D/A of electron donor/electron acceptor in the complex obtained in Example 10
was determined in the same manner as in Example 9, and was found to be 1/1.3.

Comparative Example Bisethylene dithiotetrathiafulvalene (BEDTT)
TF) (10 mg) was placed in a flask, 50 ml of benzonitrile was added thereto, and the mixture was heated to 130°C to dissolve. 100 mg of n-Bu4 NI3 was mixed with this and stirred for 10 minutes. Although the mixture was slowly cooled to room temperature, no reaction product was observed to precipitate, confirming that no complex could be formed by the direct complexation method. We also attempted to generate a complex using the direct complexation method using tetramethyltetrathiafulvalene (TMTTF) and n-Bu4NI3 in the same manner as in the case of BEDTTTF, but the direct complexation method did not produce a complex. It was confirmed that this is not possible.

[0053]

[Effects of the Invention] As described above, the present invention provides a novel organic compound that has good electron donating properties, can be directly complexed with an electron acceptor, and has excellent thermal stability. was provided. Furthermore, a conductive complex using this new organic compound as an electron donor was provided.

Claims (2)

[Claims] [Claim 1] General formula (I) [In the formula, X1a, X2a, X3a, X4a, X1b, X
2b, X3b and X4b are each independently S or Se
, Y is a polycyclic aromatic group in which two or more benzene rings are condensed or a hetero atom-containing aromatic 5-membered ring group, and Z1
a, Z2a, Z1b and Z2b each independently represent a hydrogen atom, Cn H2n+1 (n = an integer of 1 to 5), XCn
H2n+1 (X = S or Se, n = an integer of 1 to 5), or CnH2n (n = an integer of 1 to 5) or X (C
n H2n)m
b and R3b are each independently a hydrogen atom or Cn H
2n+1 (n=an integer of 1 to 5)], a thia and/or selenafulvalenyl group-containing compound. 2. An electron donor/electron acceptor obtained by using the thia and/or selenafulvalenyl group-containing compound according to claim 1 as an electron donor and reacting this electron donor with an electron acceptor. A conductive complex having a molar ratio of 1/0.1 to 1/10.