JP2006232793A - New functional electron acceptor and its functional metal complex polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional metal complex which has a new skeleton structure and good conductivity and can be used as an organic conductive material or magnetic material. <P>SOLUTION: This functional metal complex polymer obtained from a compound of formula (1) (R is H, Cl, Br, F, NO<SB>2</SB>, CN, or Ph group) as an electron acceptor and any other metal ion as an electron donor. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a highly conductive metal complex polymer or a new molecular magnetic compound using an organic receptor having a new skeletal structure that can be used for wiring such as molecular circuits and various organic conductive materials.

  Conductors and magnetic materials based on metal complex polymers have attracted attention because they are lighter than metal materials such as copper and aluminum, and do not corrode. Furthermore, since it is a substance based on a molecular skeleton compared to a metal material, it is possible to design functionality, and it is also excellent that it is manufactured using abundant resources as raw materials.

The metal complex itself is an electrical insulator, and in order to impart conductivity to the metal complex, it is common to use a charge transfer interaction between the metal ion and its organic compound site or between the organic compounds. The types of skeleton structures of organic electron acceptors that interact with metal ions are, for example, tetracyanoquinodimethane (DCNQI) (see Non-Patent Document 1) and dicyanobenzoquinone diimine (TCNQ) (see Non-Patent Document 2). Since there are only a few examples, development of an organic electron acceptor having a novel skeleton structure has been awaited.
Z. Hanhua, el. al. Inorg. Chem. 38 (1), 144-156 (1999) A. Alexander, et. al. , Angew. Chem. 98 (8), 759-761 (1986) K. M.M. Dumber et. al. Inorg. Chem. , 38, 144-156 (1999)

Problems to be solved by the invention

  However, none of the conventional organic electron acceptors for producing a conductive complex polymer can obtain good conductivity other than the DCNQI Cu complex (see Non-Patent Document 1). For this reason, many derivatives have already been synthesized and investigated, and new physical property phenomena cannot be expected.

  It is to obtain a functional metal complex polymer that can be chemically synthesized relatively easily, has a new chemical structure, and can obtain high electrical conductivity and magnetism.

Means for solving the problem

  This novel Cu-TANC high-conductivity complex exhibits completely different properties from those of Cu-DCNQI, both in terms of conductivity and magnetism, and can be adapted to the development of new materials.

（式中、Ｒは、Ｈ、Ｃｌ、Ｂｒ、Ｍｅ、ＣＮ、Ｐｈ基である）That is, the present invention is a novel organic electron acceptor represented by the following formula (1).

(In the formula, R is H, Cl, Br, Me, CN, Ph group)

（式中、Ｍは、Ｃｕ、Ａｇ、Ａｕであり、ｍは１〜３である。Ｘは、Ｆ⁻、Ｃｌ⁻、Ｂｒ

０である。ｍが１から３へ、またはｎが０．５から１．０へと移るに従って伝導体から磁性体へと変わる。）Further, the present invention is a conductive complex polymer and a functional molecular magnetic substance represented by the formula (2) in which the compound represented by the formula (1) is an electron acceptor and another metal ion is an electron donor. .

(In the formula, M is Cu, Ag, Au, and m is 1 to 3. X is F ⁻ , Cl ⁻ , Br.

0. As m shifts from 1 to 3 or n shifts from 0.5 to 1.0, the conductor changes to a magnetic substance. )

The novel organic electron acceptor (hereinafter referred to as “compound (1)”) of the formula (1) of the present invention can be easily synthesized by, for example, the method shown below.

The compound (1) of the present invention can generate a stable anion radical by one-electron reduction.

The synthesis of the electron donor of the formula (2) of the present invention (hereinafter referred to as “compound (2)”) can be easily synthesized by the following method using, for example, the compound (1) (TANC) as an electron acceptor.

The invention's effect

The highly conductive complex polymer using copper ions obtained by the present invention has high conductive properties in which d orbitals and π orbitals are entangled. For example, in the compound of the present invention, a crystal having conductivity reaching approximately 100 Scm ⁻¹ has been obtained. This has a one-dimensional structure in which the compound (1) and the copper ion are sequentially linked by a coordinate bond at 1: 1, and this chain is a two-dimensional ladder having a separate laminated type in which the compounds (1) are laminated. Because it has a type. Since the two-dimensional ladder is separated by a disordered fluorine ion layer, it has such high conductivity. Since it can be formed into a film like a TCNQ-Cu complex polymer (see Non-Patent Document 3), a switching element and a transistor function can be derived.

  The present invention begins with the synthesis of a functional electron acceptor compound (1) represented by the formula (1), which obtains a fluoroflavin derivative from quinoxaline and an orthophenylenediamine derivative, and then the compound is dissolved in toluene. It can be easily synthesized when an oxidation reaction is carried out in the presence of an oxidizing agent such as lead oxide or DDQ (2,3-dichloro-5,6-dicyanquinone). On the other hand, the electron donor compound (2) can be easily synthesized from the compound (1) and various metal ion compounds in an organic solvent.

  In the present invention, the highly conductive compound of the compound (2) is preferably a derivative of R = H, the optimum metal ion as a conductor of the compound (2) is copper, the number of TANC is m = 1, halogen The ions are preferably fluorine ions, and n is preferably 0.5.

Next, examples of the present invention will be shown and described in detail. The instrument analysis used the following instruments.
NMR: JEOL JEOL-Lambda300
IR: JASCO JASCO FT / IR-420 and PERKIN-ELMER Spectrum One
MS: JEOL JMA-700T
Elemental analysis: PERKIN-ELMER240C Elemental Analyzer
ICP: Seiko Electronics Industry SPS-7700 (ver. 1.02)
Quantification of F: DX-500 manufactured by Dionesque
Electrical conductivity measuring device: constant current generator YOKOGAWA7651
ESR: ER041MR from JEOL

9.5 g (60 mol) of 2,3-dihydroxyquinoxaline and 25 g (0.12 mol) of phosphorus pentachloride were heated at an external temperature of 170 ° C. After heating for 15 minutes, the mixture was allowed to cool to room temperature, added to 500 ml of ice water, and filtered. The obtained crystals were recrystallized from ethanol. Yield 10.8 g (92%).
MS: m / e 199 (M ⁺ )
Elemental analysis C = 48.32%, H = 2.27%, N = 13.92%
(Calculated as C ₈ H ₄ N ₂ Cl ₂ : C = 48.28%, H = 2.03%, N = 14.07%)

2.3-dichloroquinoxaline (2.00 g, 10 mmol) and o-phenylenediamine (2.16 g, 20 mmol) were added to ethylene glycol (10 ml), and the reaction was heated at an external temperature of 200 ° C. The mixture was allowed to react for 15 minutes and allowed to cool to room temperature, then added to 250 ml of hot water and filtered. After washing with ethanol, it was dried.
Yield 1.77 g (76%)
MS: m / e 235 (M +)
Elemental analysis C = 71.37%, H = 4.21%, N = 23.78%
(Calculated values as C ₁₄ H ₁₀ N ₄ : C = 71.78%, H = 4.30%, N = 23.92%)
UV-vis. (DMSO): 423 nm
IR (KBr): ν _NH 2945 ^{cm ∇1}

15 g of PbO ₂ was added to 120 ml of toluene containing 1.00 g (4.27 mol) of 5,11-dihydro-5,6,11,12-tetraazanaphthacene, and reacted at an external temperature of 120 ° C. for 20 hours. The obtained brown solution was concentrated to dryness to obtain the desired product (TANC).
Yield 0.99g (99%)
MS: m / e 233 (M ⁺ )
Elemental analysis C = 72.24%, H = 3.40%, N = 24.04%
(Calculated values as C ₁₄ H ₈ N ₄ : C = 72.40%, H = 3.47%, N = 24.12%)
UV-vis. (MeCN): 460 nm, 402 nm
¹ H-NMR (CDCl ₃ , TMS): δ 7.98 (m, 4H, 4th and 5th positions) δ8.43 (m, 4H, 3rd and 6th positions)
Cyclic voltammetry: E ¹ _1/2 = −0.20 V, E ² _1/2 = −0.88 V ΔE _1/2 = 0.68 V (vs. Ag _/ AgCl)
Measurement conditions: Ar atmosphere, concentration 10 ⁻³ M
Scan speed: 100 mV / s
Supporting electrolyte: ⁿ Bu ₄ NPF ₆ (0.1 M)
Working electrode: Glassy carbon
Counter electrode: Pt wire
Reference electrode: Ag / AgCl
Solution: MeCN
The half-wave potential of ferrocene taken under the same conditions is as follows.
E _1/2 = + 0.44 V (vs. Ag _/ AgCl)

N-BuLi hexane solution in which TANC (0.17 g, 0.5 mol) and 5,11-dihydro-5,6,11,12-tetraazanaphthathene (0.17 g, 0.50 mol) under Ar were cooled to -85 ° C. When added to tetrahydrofran (30 ml) containing (1.0 ml, 1.57 mmol), a dark green powder was produced.
Elemental analysis C = 63.34%, H = 5.13%, N = 15.64%
(Calculated as Li · C ₁₄ H ₈ N ₄ · (H ₂ O) · (THF) _1.25 : C = 63.34%, H = 4.76%, N = 15.55%)
ESR: g = 2.00

40 mg (0.17 mmol) of TANC and 34 mg (1.0 mmol) of tetrafluorotetraacetonitrile copper (I) were added to a mixed solution of acetonitrile / methanol and slowly concentrated at room temperature. Dark blue crystals were isolated from the solution.
Yield 25 mg (50%)
Elemental analysis C = 55.33%, H = 2.64%, N = 18.41%, Cu = 20.73%, F = 3.40%
Calculated as (C ₁₄ H ₈ N ₄ CuF _0.5 ): C = 55.08%, H = 2.64%, N = 18.35%, Cu = 20.81%, F = 3.11 %)
UV-vis. (KBr): 227 nm, 313 nm, 394 nm, 609 nm
Conductivity measurement 75Scm- ¹ (25 ° C)
Measurement conditions: DC four-terminal method (carbon paste, Au wire (φ10 μm))

23 mg (0.1 mmol) of TANC and 9.5 mg (0.05 mmol) of CuI were added to the acetonitrile solution and allowed to stand. Dark blue crystals were isolated from the solution.
Elemental analysis C = 40.48%, H = 1.83%, N = 13.22%, Cu = 14.39%
(Calculated values as (C ₁₄ H ₈ N ₄ CuI): C = 39.78%, H = 1.91%, N = 13.25%, Cu = 15.03%)
UV-vis. (KBr): 234 nm, 314 nm, 377 nm, 729 nm
ESR: active
Q band (powder method)

FIG. 1 shows that the resistance value of the compound (2) (R = H, M = Cu, m = 1, X = F, n = 0.5) decreases from room temperature (˜50 Scm ⁻¹ ) to low temperature. It shows a typical semiconductor behavior, and a transition seen as MI (metal-insulator transition) is seen at 280K. In addition, the activation energy changed from 150 meV to 45 meV at 40K.

FIG. 2 shows an ESR spectrum of Compound (2) (R = H, M = Cu, m = 1, X = I, n = 1.0) at 10K. For Cu + complexes with electron configuration d ^10, the peak of the ESR is not usually observed, the charge transfer interaction with the TaNC, can be observed a peak of radicals are generated ESR.

  The functional metal complex compound having conductivity produced from the functional electron acceptor obtained by the present invention has high conductivity, and as a result, can be used for wiring materials and conductive materials for molecular circuits. Further, the obtained conductor is stable and can be formed into a film.

  A complex of another metal ion and TANC can behave as a magnetic substance due to the interaction between the anion radical and the spin of the metal ion. Again, film formation can be performed and it can be used as a magnetic device.

It is a graph which shows the temperature change of the electronic conductivity of the compound (2) (R = H, M = Cu, X = F, n = 0.5) of this invention. FIG. 2 shows an ESR spectrum of Q band of the compound (2) of the present invention (R = H, M = Cu, m = 1, X = I, n = 1.0). (10K)

Claims (5)

The functional electron acceptor compound shown by Formula (1).

(Wherein R is H, Cl, Br, F, NO ₂ , CN, Ph group) A functional metal complex polymer represented by the formula (2) synthesized from the TANC compound represented by the formula (1) as an electron acceptor and an electron donor metal ion as another component.

(In the formula, M is Cu, Ag, Au, and m is 1 to 3. X is F ⁻ , Cl ⁻ , Br ⁻ ,

It is. ) A functional metal complex in which M is Cu, X is F, and n is 0.5, the conductivity represented by the formula (2) obtained from TANC shown in claim 2 and having a conductivity of ~ 100 Scm ^-1. High molecular.   A functional metal complex in which M having a magnetic substance represented by the formula (2) obtained from TANC shown in claim 2 is Cu, m is 1, X is I, and n is 1.0. High molecular.   A switching element and a magnetic element obtained by forming a functional metal complex polymer represented by the formula (2) obtained from TANC shown in claim 2 into a film.

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