WO2013042787A1 - Organic itinerant magnetic compound, process for producing organic itinerant magnetic compound, magnet, spintronic element, and material for hydrogen refining - Google Patents

Abstract

Provided is, for example, a compound which can be a material that renders many functions controllable. One aspect of the present invention resides in an organic itinerant magnetic compound characterized in that the compound is formed by causing organic molecules as a donor to form a salt with an inorganic acid or inorganic base and that the compound self-stacks. Another aspect of the invention resides in the organic itinerant magnetic compound of claim 1 which is characterized by having ammonium moieties. Still another aspect of the invention resides in the organic itinerant magnetic compound of claim 2 which is characterized in that the ammonium moieties of the compound in the self-stacked state are caused to form hydrogen bonds.

Description

Organic itinerant magnetic compound, method for producing organic itinerant magnetic compound, magnet, spintronic device, and hydrogen purification material

The present invention relates to an organic itinerant magnetic compound, a method for producing an organic itinerant magnetic compound, a magnet, a spintronic device, and a hydrogen purification material.

Si-based amorphous semiconductors currently occupy most of the market due to their excellent processability. For example, Si-based amorphous semiconductors are frequently used in TFTs (Thin Film Transistors) for liquid crystal displays and solar cells.

On the other hand, organic semiconductors are expected to be applied to wearable devices because of their light weight and flexibility. However, mainly in the semiconductor part, inorganic crystals or doped polymers are the mainstream, and the development of organic semiconductors such as organic amorphous semiconductors has been remarkably delayed even in the world.

In addition, the development of organic thin-film solar cells and organic EL (Organic Electro-Luminescence) devices using low-molecular π compounds and photoconductive doped polymers is currently underway, but their performance is in comparison with inorganic Si-based amorphous solids. It is well known that it is inferior. This is related to the fact that high performance and stability cannot be maintained in processing forms such as thin films and chips. Organic compounds such as organic amorphous solids are expected to have high potential from an industrial point of view, such as inorganic Si-based amorphous materials that do not depend on the processing form and have high performance, but very few examples have been applied so far. . What is known as an organic amorphous solid is limited to similar π-electron starburst molecules, and some of these radicals exhibit conductivity, but their values are generally very low. It is.

Furthermore, since a general charge transfer type organic conductor is prepared by electrolysis or the like, it is difficult to control the arrangement. In addition, since the electronic properties greatly depend on the crystal structure, there is a difficulty in application to a thin film by polymerization or liquid crystal which is required for industrialization.

Moreover, since it is difficult to control the arrangement of a conductive polymer that becomes a semiconductor by doping, it is difficult to improve the charge separation performance. Moreover, it lacks chemical stability and is deteriorated with time.

InSc and GaAs crystals having a high Hall effect are rare metals and are expensive and have poor workability. Cobalt oxide crystals known as thermoelectric materials are also difficult to reduce in weight and thickness.

From these viewpoints, a compound that can be a material capable of controlling many functions has recently been proposed (Patent Document 3). This is an organic semiconductor that can be produced by a simple technique in which a donor molecule is salted with an inorganic acid or an inorganic base. It is expected that various organic semiconductors can be manufactured by the same method, and this method is a breakthrough.

JP2005-112951 Special table 2007-526640 PCT / JP2009 / 52440

The present invention has been made in view of the above-described background art, and an object thereof is to provide a compound that can be a material capable of controlling many functions.

According to this invention, in order to achieve the above-mentioned object, the configuration as described in the claims is adopted. Hereinafter, the present invention will be described in detail.

The first aspect of the present invention is
Formed by salting organic molecules that serve as donors with inorganic acids or bases,
It is an organic itinerant magnetic compound characterized by self-assembly.

The second aspect of the present invention is
2. The organic itinerant magnetic compound according to claim 1, which has an ammonium moiety.

The third aspect of the present invention is
3. The organic itinerant magnetic compound according to claim 2, wherein hydrogen bonds are made to the ammonium moiety in a self-assembled state.

The fourth aspect of the present invention is
An organic itinerant magnetic compound characterized in that it is formed by derivatizing a compound having a tetrathiafulvalene analog moiety in the skeleton and having a protonic acid functional group into a salt with ammonia or a salt with hydroxyamine .

The fifth aspect of the present invention provides
The organic itinerant magnetic compound is characterized in that it is formed by inducing a compound having a primary amine with a tetrathiafulvalene analog moiety in the skeleton into an inorganic acid salt.

The sixth aspect of the present invention provides
An organic itinerant magnetic compound characterized by being any one of the compounds represented by (Chemical Formula 1).

(In the formula, X1 to X4 are either S or Se, and R1 is any one represented by (Chemical Formula 2).) (In the formula, R2 to R8 are any one represented by (Chemical Formula 3) (same or different) May be.)

The seventh aspect of the present invention provides
It is an organic itinerant magnetic compound characterized by being any compound represented by (Chemical Formula 4).

The eighth aspect of the present invention is
It is an organic itinerant magnetic compound characterized by being any compound represented by (Chemical Formula 5).

The ninth aspect of the present invention provides
An organic itinerant magnetic compound characterized by being tetrathiafulvalene-2-carboxylic acid / ammonium salt.

The tenth aspect of the present invention provides
A method for producing an organic itinerant magnetic compound is characterized in that an organic molecule serving as a donor is formed by salt formation with an inorganic acid or an inorganic base on a one-to-one basis to produce a self-assembling compound.

The eleventh aspect of the present invention is
An organic itinerant magnetic compound characterized by having a pseudo-closed shell configuration.

The twelfth aspect of the present invention is
Including salt bridge bonds,
It is an organic itinerant magnetic compound formed by adding a Brönsted acid or base to an organic compound having a molecular weight of 20000 or less and stably generating 0.1% or more radical species.

The thirteenth aspect of the present invention is
A salt bridge material having multiple bonds that can be protonated in an electron donor molecule or in an electron acceptor molecule;
It is an organic itinerant magnetic compound formed by stable generation of 0.1% or more of radical species in the formation of salt bridges.

The fourteenth aspect of the present invention provides
A salt bridge substance having a tetrathiafulvalene skeleton or a tetraselenafulvalene skeleton,
It is an organic itinerant magnetic compound formed by the stable generation of 5% or more radical species in the formation of salt bridges.

The fifteenth aspect of the present invention is
15. The organic itinerant magnetic compound according to claim 13, wherein the electronic state of the radical spin has a quasi-closed shell configuration.

The sixteenth aspect of the present invention is
A method for producing an organic itinerant magnetic compound containing a salt bridge bond,
The present invention relates to a method for producing an organic itinerant magnetic compound formed by adding a Bronsted acid or a base to an organic compound having a molecular weight of 20000 or less and stably generating 0.1% or more radical species.

The seventeenth aspect of the present invention is
A method for producing an organic itinerant magnetic compound which is a salt bridge substance having multiple bonds that can be protonated in an electron donor molecule or an electron acceptor molecule,
The present invention relates to a method for producing an organic itinerant magnetic compound formed by stably generating 0.1% or more radical species in the formation of a salt bridge.

The eighteenth aspect of the present invention provides
A method for producing an organic itinerant magnetic compound which is a salt bridge substance having a tetrathiafulvalene skeleton or a tetraselenafulvalene skeleton,
The present invention relates to a method for producing an organic itinerant magnetic compound formed by stably generating 0.1% or more radical species in the formation of a salt bridge.

The nineteenth aspect of the present invention provides
19. The method for producing an organic itinerant magnetic compound according to claim 17, wherein the electronic state of the radical spin has a pseudo-closed shell configuration.

The twentieth aspect of the present invention provides
10. The organic itinerant magnetic compound according to claim 9, which is a semiconductor.

The 21st aspect of the present invention is
10. The organic itinerant magnetic compound according to claim 9, which is a ferromagnetic material.

The twenty-second aspect of the present invention provides
10. The organic itinerant magnetic compound according to claim 9, which is an organic room temperature itinerant magnetic compound.

The twenty-third aspect of the present invention provides
A magnet containing the organic itinerant magnetic compound according to claim 9.

The twenty-fourth aspect of the present invention provides
A spintronic device comprising the organic itinerant magnetic compound according to claim 9.

The 25th aspect of the present invention is
It exists in the hydrogen purification material containing the organic itinerant magnetic compound of Claim 9.

The twenty-sixth aspect of the present invention provides
An organic compound containing a proton defect in a salt bridge bond, which generates a radical cation or a radical anion to compensate for the lost charge.

The twenty-seventh aspect of the present invention provides
This is an organic itinerant magnetic compound that generates radical cations or radical anions to compensate for the lost charges due to the abundance ratio of cation and anion deviating from 1: 1 in the salt bridge material.

The 28th aspect of the present invention provides
2. The organic itinerant magnetic compound according to claim 1, which produces a negative magnetoresistance effect.

The 29th aspect of the present invention provides
7. The organic itinerant magnetic compound according to claim 6, which produces a negative magnetoresistance effect.

The thirtieth aspect of the present invention is
10. The organic itinerant magnetic compound according to claim 9, which produces a negative magnetoresistance effect.

The thirty-first aspect of the present invention provides
10. The organic itinerant magnetic compound according to claim 9, which produces a substantially linear negative magnetoresistance effect according to an applied magnetic field.

The thirty-second aspect of the present invention provides
32. The organic itinerant magnetic compound according to claim 31, wherein the magnetoresistive effect increases as the temperature decreases.

The thirty-third aspect of the present invention provides
32. The organic itinerant magnetic compound according to claim 31, wherein the magnetoresistive effect increases as the temperature becomes lower in a temperature range of 250K to 300K.

Here, examples of the protonic acid functional group include —COOH, —SO ₃ H, —PO ₃ H, and —PSO ₂ H. The primary amine is represented by, for example, —NH _n D _3-n (n = 2 to 0) (where D is deuterium). Examples of the inorganic acid include HBF ₄ , HClO ₄ , HCl, HBr, HI, DBF ₄ , DClO ₄ , DCl, DBr, and DI. Examples of inorganic bases include NH _n D _3-n (n = 3-0), NH _n D _2-n OH (n = 2-0), NH _n D _2-n OD (n = 2-0). is there.

Note that a semiconductor refers to a substance that exhibits an intermediate property between a conductor that conducts electricity and an insulator that does not conduct electricity. For example, the electrical conductivity is in the range of approximately 10 ² to 10 ⁻⁶ Scm ⁻¹ (S is Ω ⁻¹ ) near room temperature.

The donor refers to an electron donor (electron donating molecule or electron donating group). The acceptor refers to an electron acceptor (electron acceptor molecule or electron acceptor group).

Room temperature refers to 300K (27 ° C), and near room temperature means about ± 10 ° C.

Containing tetrathiafulvalene (TTF) analog moiety in the skeleton means tetrathiafulvalene in the skeleton of the molecule, such as 1- (dibenzotetrathiafulvalen-2-yl) ethylamine and tetrathiafulvalene-2-carboxylic acid. It has a structure.

In addition, the compounds in the present specification and claims include compounds having an equivalent structure and having an element substituted with an element isotope such as deuterium. Therefore, for example, the above (Chemical Formula 2) includes the following (Chemical Formula 2A).

According to the present invention, a compound that can be a material capable of controlling many functions can be obtained. Other objects, features, or advantages of the present invention will become apparent from the detailed description based on the embodiments of the present invention described later and the accompanying drawings.

It is a figure which shows the binding energy of N (1s) measured by the photoelectron spectroscopy (X-rayphotoelectron | spectroscopy * (XPS) *) of tetrathiafulvalene-2-carboxylic acid ammonium salt. Band structure of tetrathiafulvalene-2-carboxylic acid ammonium salt a) Band dispersion b) 状態 Density of states near Fermi level It is a figure which shows the temperature dependence of the magnetization curve of tetrathiafulvalene-2-carboxylic acid ammonium salt. It is a figure which shows the surface analysis by XPS of tetrathiafulvalene-2-carboxylic acid ammonium salt. It is a figure which shows the optical absorption spectrum of the tetrathiafulvalene-2-carboxylic-acid ammonium salt pellet sample. It is a figure which shows the magnetization curve of deuterated tetrathiafulvalene-2-carboxylic acid ammonium salt. It is a figure which shows the proton electromotive force of tetrathiafulvalene-2-carboxylic acid ammonium salt and deuterated tetrathiafulvalene-2-carboxylic acid ammonium salt. It is a figure which shows the hydrogen concentration battery method. It is a figure which shows the magnetization curve of tetrathiafulvalene-2-carboxylic acid hydroxyammonium salt. It is a figure which shows the magnetization curve of dibenzotetrathiafulvalene ethane ammonium bromide. It is a figure which shows the magnetization curve of dibenzotetrathiafulvalene ethane ammonium tetrafluoride salt. It is the figure which plotted the remanent magnetization in 300K and 0 magnetic field of three kinds of compounds with different radical spin concentrations. The inset diagram shows that a sufficiently effective magnetic moment is developed at a spin concentration of 0.1% or more. It is a figure which shows the correlation with the spin concentration of the solvent used in the case of crystallization of ammonium salt, and the obtained carrier dope crystal | crystallization. It is a schematic diagram which shows the crystal structure in 300K. It is a figure which shows the temperature dependence of electrical conductivity. It is a figure which shows a thermoelectromotive force. It is a figure which shows the calorimetric measurement result of differential scanning calorimetry (Differential Scanning Calorimeter (DSC)). It is a figure which shows the thermogravimetric measurement result by a thermogravimetric analyzer (Thermogravimetric analyzer (TGA)). It is a figure which shows a dielectric constant. It is a figure which shows the measurement data at the time of measuring photoconductivity, changing temperature. It is a figure which shows the measurement data at the time of measuring photoconductivity, changing temperature. It is a figure which shows the measurement data at the time of measuring photoconductivity, changing temperature. It is a figure which shows a thermoelectromotive force. It is a figure which shows the temperature dependence of electrical conductivity. It is a figure which shows the temperature dependence of electrical conductivity. It is a figure which shows a diffuse reflection spectrum. It is a figure which shows the temperature dependence of a thermoelectromotive force. It is a figure which shows the diffuse reflection spectrum of each compound. This is a powder X-ray crystal structure analysis of tetrathiafulvalene-2-carboxylic acid / ammonium salt. This is a powder X-ray crystal structure analysis of deuterated tetrathiafulvalene-2-carboxylic acid / ammonium salt. It is a schematic diagram which shows the three-dimensional structure which paid its attention to the intermolecular bond and the intermolecular interaction. It is a schematic diagram which shows the three-dimensional structure which paid its attention to the intermolecular bond and the intermolecular interaction. TTFCOO · NH ₄ salt shows the electronic state by the unrestricted Hartree-Fock method (UHF) / 6-31G * using a model in which one molecule of the radical species TTF ^{· +} COO · NH ₄ is buried in the tetramer FIG. It is a figure which shows the result of the periodic quantum chemical calculation performed in consideration of the periodicity of a hydrogen bond direction (one-dimensional) with respect to the cluster model which contains one radical seed | species in 4 molecular units. TTFCOO ^- is a diagram showing the external magnetic field dependency example (temperature 300K) of the electrical conductivity of the NH ₄ ⁺ salt. TTFCOO ^- is a diagram showing a magnetoresistance measurement example (temperature 300K) of NH ₃ ⁺ OH salts single crystal samples. TTFCOO ^- is a diagram showing temperature dependence of the magnetoresistive effect of the NH ₃ ⁺ OH salts single crystal samples. TTFCOO ^- is a diagram showing a magnetoresistance measurement example (temperature 300K) of NH ₃ ⁺ Ph salt. TTFCOO ^- is a diagram showing temperature dependence of the magnetoresistive effect of the NH ₃ ⁺ Ph salt. _{DBTTF (CH) (CH 3)} NH 3 + · Br - is a diagram showing a magnetoresistive measurement example (temperature 300K) salts.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[Overview]

The magnetic interaction of pure organic solids is generally very weak, and any ferromagnetic properties appear only at very low temperatures of about 7K or less. However, the carrier-doped organic matter developed by the present inventors produces some itinerant electrons that behave ferromagnetically in a wide temperature range from extremely low temperature to room temperature. The technique described in the present embodiment strongly suggests the possibility of realizing an organic magnet at room temperature that is the first in the world if the proportion of ferromagnetic itinerant electrons in a material can be increased synthetically. It is also expected to be applied to room temperature spintronics because it is a room-temperature itinerant magnet that is rarely seen in organic materials. Furthermore, since it has proton conductivity, it can be applied to hydrogen purification materials from room temperature organic fuel cells and natural gas.

Here, two examples are briefly shown as specific examples.

1) After tetrathiafulvalene-2-carboxylic acid was obtained from tetrathiafulvalene (TTF) in two steps in a total yield of 65%, a salt was prepared with a 28% aqueous ammonia solution, and pure 1: 1 tetrathiafulvalenylcarboxylic acid / ammonium salt was obtained.

The electrical conductivity when the obtained powdered solid was pelletized was about 1.0 × 10 ⁻³ S / cm at room temperature.

2) Using ethyl methyl ketone as a starting material, dibenzotetrathiafulvalenylethylamine was obtained in 15 steps in a total yield of 1%, and then salted with 42% aqueous tetrafluoroboric acid solution or 47-49% aqueous bromic acid solution. Prepared to obtain 1: 1 dibenzotetrathiafulvalenylethylamine tetrafluoroborate and dibenzotetrathiafulvalenylethylamine bromate, both of which were pure at the elemental analysis level.

The electrical conductivity when the obtained powdery amorphous solid was pelletized was about 1.0 × 10 ⁻³ to 10 ⁻⁴ S / cm at room temperature.

Next, an outline of the molecular assembly structure of tetrathiafulvalene-2-carboxylic acid / ammonium salt will be described.

In the high temperature region above 200K, a new characteristic that has never been seen before was observed in that a high thermoelectromotive force was generated by the mechanism derived from the rotation and vibration of the ammonium moiety. When counter cations that do not have hydrogen-bonding ability for the ammonium moiety and a part of the ammonium proton are replaced with substituents, the rotation properties of ammonium are the key to physical properties because they do not exhibit very good physical properties. It has been proved experimentally.

Regarding electrical conduction, it is clear that hydrogen bonds are involved in electron conduction from the frequency dependence of dielectric dispersion of deuterated samples.

Ammonium is not only the key to physical properties, but also plays a role in effectively self-assembling TTF (donor) molecules into a molecular arrangement suitable for the carrier transport phenomenon.

First, the crystal structure at 300K will be described as an example.

FIG. 12 is a schematic diagram showing a crystal structure at 300K. As shown in the figure, a columnar hydrogen bond network is formed with ammonium as the center, and the π-π interaction and S ... S contact are generated by stacking them in a nested manner. The carrier can move around in a two-dimensional array.

Hereinafter, the physical properties of these compounds will be described in detail while exemplifying specific compounds. These compounds are primarily organic materials that are carrier-doped to compensate for the loss of proton defects that occur in salt bridge bonds.

[Itinerant ferromagnet]

FIG. 1 is a diagram showing the bond energy of N (1s) of tetrathiafulvalene-2-carboxylic acid ammonium salt. The amount of proton defects contained in ammonium tetrathiafulvalene-2-carboxylate, which is the most representative substance, is estimated to be 15% from the mixing ratio of NH ₃ species in the nitrogen 1s orbital by photoelectron spectroscopy (XPS). This almost coincides with the tetrathiafulvalene radical molecule content of 16% estimated from the electron spin resonance method. The presence of this proton defect causes spin polarization in the electrons in the crystal.

FIG. 2 shows the band structure of tetrathiafulvalene-2-carboxylic acid ammonium salt a) band dispersion b) density of states near the Fermi level c) spin polarization orbit. FIG. 2a shows the band dispersion of the ground state of the crystal structure based on the unit cell of tetrathiafulvalene-2-carboxylic acid ammonium salt optimized by the first principle calculation. K space is considered 4x4x4 size. Here, a 16% doping effect is added as a background charge. This is a square lattice with large dispersion in the a-axis and b-axis, and its shape differs between up and down spins. FIG. 2b shows that the up-spin and down-spin state densities at the Fermi level are different. These indicate that spin polarization occurs in itinerant electrons that contribute to electron conduction. The magnitude of the magnetization is 0.66μ _B. This calculation clearly shows that when proton defects are uniformly arranged in this material, it becomes an itinerant ferromagnet at room temperature. However, similar calculations have shown that hydrogen-bonded protons are mobile and the degree of metastable spin polarization that occurs during proton transfer is small, which reduces the actual magnetic interaction. It is a factor.

FIG. 3 shows the magnetization curve of a sample obtained by pressure-molding tetrathiafulvalene-2-carboxylic acid ammonium salt crystal. Diamagnetic correction is not performed. Residual magnetization has been confirmed over a wide temperature range from 5K to 400K, indicating the presence of ferromagnetic interactions. The tendency of soft magnets with small coercive force is shown from the shape of the magnetization curve.

FIG. 4 shows the results of surface analysis by XPS. XPS detects the presence of very small amounts of metal impurities attached to the sample surface. However, since elements other than organic substances are not detected over a wide range by multiple measurements, it can be said that the above-mentioned magnetic properties are derived from itinerant electrons of tetrathiafulvalene-2-carboxylic acid ammonium salt. The size of the magnetic moment of saturation magnetization is significantly smaller than 10 ^-4 mu _B and theoretical values, which is that incorporation of proton defect is not a favorable uniform conditions for expressing the magnetic interaction Is considered to be the biggest cause. In addition, by making the powder microcrystals into a pellet shape pressurized at 9 MPa / cm ² for 2 minutes, the uniformity of the proton defect mixing state inside the crystal increases and the magnetic susceptibility tends to increase.

FIG. 5 is a diagram showing an optical absorption spectrum of a tetrathiafulvalene-2-carboxylic acid ammonium salt pellet sample. The change in the electronic state is also apparent from the difference in the optical absorption spectrum between the powder crystallite and the pellet state shown in the figure.

FIG. 6 is a diagram showing a magnetization curve of deuterated tetrathiafulvalene-2-carboxylic acid ammonium salt.

FIG. 7 is a graph showing proton electromotive forces of tetrathiafulvalene-2-carboxylic acid ammonium salt and deuterated tetrathiafulvalene-2-carboxylic acid ammonium salt. Furthermore, tetrathiafulvalene-2-carboxylic acid ammonium salt and deuterated tetrathiafulvalene-2-carboxylic acid ammonium salt generate proton electromotive force of about half and 1/4 of Nernst's theoretical formula, respectively, by the hydrogen concentration cell method. Therefore, both have proton conductivity (FIG. 7A).

The table shows the measurement conditions at this time.

FIG. 7B is a diagram showing the hydrogen concentration cell method.

This is a characteristic that can be applied to hydrogen purification from fuel cells and natural gas.

FIG. 8 is a diagram showing a magnetization curve of tetrathiafulvalene-2-carboxylic acid hydroxyammonium salt. FIG. 9 is a diagram showing a magnetization curve of dibenzotetrathiafulvaleneethane ammonium bromide. Each of these figures shows the magnetization curves of different types of carrier-doped organic materials. Differences in the magnitude of the magnetic moment due to differences in the amount of proton defects and the crystal arrangement, but all are basically room temperature itinerant magnets, similar to the mechanism of magnetic properties of tetrathiafulvalene-2-carboxylic acid ammonium salt It is thought that magnetic interaction is expressed by the mechanism.

FIG. 10A is a diagram showing a magnetization curve of dibenzotetrathiafulvaleneethaneammonium tetrafluoride salt.

In particular, the following organic organic magnetic compound is preferable.

1. A salt bridge substance having a tetrathiafulvalene skeleton and a tetraselenafulvalene skeleton, in which 0.1% or more of the radical species are stably generated when the salt bridge is formed. The radical spin electronic state has a quasi-closed shell configuration.

The basis for this is that when a radical spin occurs at a concentration of 0.1% or higher and the electronic state has a pseudo-closed-shell configuration, electrons on the radical spin move as itinerant electrons, and electrons of about 10 ^-5 S / cm or higher. This is because it has been confirmed by experiments that conductivity is exhibited.

FIG. 10B is a plot of the residual magnetization in a 300K, 0 magnetic field for three compounds with different radical spin concentrations. The compounds are A (tetrathiafulvalenecarboxylic acid: 0%), B (tetrathiafulvalenecarboxylic acid aniline salt single crystal: 2%), and C (tetrathiafulvalenecarboxylic acid hydroxyamine salt single crystal: 10%), respectively. . From this figure, it can be seen that it is preferable to generate at least 0.1% or more radical spins in order to obtain effective magnetic properties.

Organic radical species are highly reactive because the electronic state of radical spin is at the HOMO level, and they tend to decompose due to external factors such as oxygen in the air. Therefore, in order to make the organic radical species into a chemically stable electronic state, ingenuity is generally made to introduce an electron-withdrawing group such as a cyano group or a nitro group into the molecule for stabilization. In this way, even if the electronic state is devised and stored in the air for a long time, the composition and electronic state of the molecule at the beginning of the synthesis are maintained, and a state in which radical spin that does not easily decompose occurs is generated. Is expressed here.

The d orbitals of transition metal elements and the f orbitals of rare earth metal elements are atomic orbitals with higher localization located in the inner shell than the s or p orbit of the outermost shell, and have lower orbital energy. The electronic state of this d orbital or f orbital is called a quasi-closed shell configuration, but because of the high localization of these orbitals, the d and f electrons occupied there tend not to participate in chemical bonds, so Stabilize. The pseudo-shell configuration, not participating in chemical bonds, and strongly stabilized odd-electron properties often cause magnetism. The pseudo closed shell arrangement will be described later.

When radical spin occurs at a concentration of 0.1% or more, electrons on the radical spin move as itinerant electrons and exhibit electron conductivity. However, 1% or more is more preferable because of a decrease in non-essential electronic conductivity due to grain boundary resistance in the polycrystalline sample. Further, it is more preferably 5% or more for the reason that a sufficiently large magnetic property can be exhibited even in a polycrystalline sample.

2. A salt bridge substance having multiple bonds that can be protonated in an electron donor or electron acceptor molecule, and stable generation of radical species of 0.1% or more of the whole when forming a salt bridge. More preferably, the electronic state of the radical spin has a quasi-closed shell configuration.

The basis for this is that when a radical spin occurs at a concentration of 0.1% or higher and the electronic state has a pseudo-closed-shell configuration, electrons on the radical spin move as itinerant electrons, and electrons of about 10 ^-5 S / cm or higher. This is because it has been confirmed by experiments that conductivity is exhibited.

3. A substance that contains a salt bridge bond and stably generates more than 0.1% of radical species by adding a Bronsted acid or base to a low molecular weight organic compound having a molecular weight of 20000 or less. More preferably, the electronic state of the radical spin has a quasi-closed shell configuration.

The reason for this is that, when radical spin is generated at a concentration of 0.1% or more, it is confirmed by experiments that electrons on the radical spin move as itinerant electrons and show electron conductivity.

Even if it is a polymer, it preferably has a part of self-assembly by salt bridges, and a molecular weight of 20000 or less is desirable to satisfy this. In order to fully exhibit magnetic properties, it is desirable that proton defects are uniformly introduced into the material and a uniform dope state is obtained, and it is assumed that the difficulty increases at an extremely large molecular weight. More preferably, the molecular weight is 10,000 or less.

[Other physical properties]

If the properties of the semiconductor and the magnetic material can be fused, it can be used as a ferromagnetic semiconductor. This fusion shows the feasibility of spintronic devices and is important. Here, what is related to the properties as a semiconductor is mainly described. First, the physical properties of the following compounds will be described.

FIG. 13 is a diagram showing temperature dependence of electrical conductivity. The 4-terminal method was used for measurement.

FIG. 14 is a diagram showing the thermoelectromotive force. As shown in the figure, even when the temperature is changed from low temperature to high temperature or from high temperature to low temperature, no change due to phase transition is observed, indicating that the temperature dependence of resistivity is a thermally activated semiconductor. Further, the thermoelectromotive force has almost no temperature dependence, and it can be seen that this compound has excellent physical properties in a wide temperature range. In particular, this data shows that application to thermoelectric power generation using the thermoelectric effect can be expected.

FIG. 15 is a diagram showing a calorimetric measurement result of differential scanning calorimeter (DSC). FIG. 5 is a diagram showing a thermogravimetric measurement result by a thermogravimetric analyzer (TGA). All measured values were almost stable up to 140 ° C or lower, but the measured values changed greatly after exceeding 140 ° C. This seems to suggest that NH ₃ is lost when the temperature exceeds 140 ° C.

FIG. 16 is a diagram showing a dielectric constant. As shown in the figure, polarization and dielectric response were observed. This result suggests the possibility of application as a ferroelectric memory and, consequently, an actuator utilizing the piezoelectric effect due to the ferroelectricity.

17, FIG. 18 and FIG. 19 are diagrams showing measurement data when the photoconductivity is measured while changing the temperature. 18, 19 and 20 show data obtained when measurement was performed at 0 ° C., 20 ° C., and 30 ° C., respectively. A pelleted sample (width 0.08 cm, thickness 0.03 cm) was used, and a two-terminal method was used in which terminals were attached with silver paste. Further, light irradiation in a wavelength region including the entire visible light region was performed.

Next, the physical properties of the following compounds will be described.

FIG. 21 is a diagram showing a thermoelectromotive force. Similar to the above-described compound, even when the temperature is changed from low temperature to high temperature or from high temperature to low temperature, no change due to phase transition is observed, indicating that the temperature dependence of resistivity is a thermally active semiconductor. Further, it is understood that there is almost no temperature dependence of the thermoelectromotive force, and this compound has excellent physical properties in a wide temperature range. This data also shows that this compound can be expected to be applied to thermoelectric power generation utilizing the thermoelectric effect.

Next, the physical properties of the following compounds will be described.

FIG. 22 is a diagram showing temperature dependence of electrical conductivity. On the other hand, FIG. 23 is a graph showing the temperature dependence of the electrical conductivity of the compound of formula 6. As shown in the figure, the temperature dependence of the electrical conductivities of the two is very similar, suggesting that they exhibit similar physical properties in other respects.

FIG. 24 is a diagram showing the temperature dependence of electrical conductivity. On the other hand, FIG. 23 is a graph showing the temperature dependence of the electrical conductivity of the compound of formula 6. As shown in the figure, the temperature dependence of the electrical conductivities of the two is very similar, suggesting that they exhibit similar physical properties in other respects.

FIG. 25 is a diagram showing the temperature dependence of the thermoelectromotive force. Like FIG. 14 and FIG. 21, it shows a high thermoelectromotive force and has little temperature dependence, which indicates that this compound also has excellent physical properties. This data also shows that this compound can be expected to be applied to thermoelectric power generation utilizing the thermoelectric effect.

FIG. 26 is a diagram showing a diffuse reflection spectrum of each compound. As shown in the figure, each compound was found to have absorption up to about 900 nm, unlike ordinary acid / base salts. This indicates that absorption of long-wavelength electromagnetic waves has been realized, indicating that these compounds are suitable for applications such as solar cells.

The following compounds were classified into two groups based on electrical conductivity.

1) Group with electrical conductivity ~ 10 ^-2 S / cm

2) Group with electrical conductivity ~ 10 ^-3 S / cm

[Molecular assembly structure]

FIG. 27 is a powder X-ray crystal structure analysis of tetrathiafulvalene-2-carboxylic acid / ammonium salt. FIG. 28 is a powder X-ray crystal structure analysis of deuterated tetrathiafulvalene-2-carboxylic acid / ammonium salt. All were measured using synchrotron light under conditions of 1.3000 angstroms. By analyzing these, it is clear that tetrathiafulvalene-2-carboxylic acid / ammonium salt is in a microcrystalline state having a certain regularity in its molecular assembly structure.

FIG. 29 and FIG. 30 are schematic diagrams showing a three-dimensional structure focusing on intermolecular bonds and intermolecular interactions. As shown in the figure, compounds such as tetrathiafulvalene-2-carboxylic acid / ammonium salt overlap each other, and there are many loose bonds due to hydrogen bonds between the molecules, and the TTF sites are arranged in a column as a whole. is doing. The contact distance between S atoms and S atoms is 3.5 angstroms or less, and the orbits of adjacent S atoms overlap to maintain a stable three-dimensional structure.

[Pseudo closed shell arrangement]

The pseudo-closed-shell arrangement is realized by a simple technique of embedding organic radical species between closed-shell molecular arrays by self-assembly using a hydrogen bond network consisting of an acid and a base, which is the key to carrier generation. The quasi-closed-shell configuration is, for example, an electron configuration found in transition metal d orbitals and particularly rare earth metal f orbitals. In this configuration, spin does not participate in chemical bonds and is low. Since it has orbital energy and is shielded by electrons in other high energy states, it is isolated and localized inside the atomic orbital. This induces a strong electron correlation effect in the solid state and becomes a source of various high physical properties specific to the strongly correlated metal. This system is also called a “heavy electron system” because it increases the effective mass of electrons due to the strong electron correlation effect. The series of compounds that have been described so far are positioned as f-electron metals that have been realized for the first time in organic solids.

This is supported by theoretical calculations. Based on the atomic coordinates of the TTFCOO · NH ₄ salt obtained from the powder X-ray crystal structure, ab using a cluster model in which one organic radical species is embedded by hydrogen bonding in 2 to 60 atoms. Initio calculation (quantum chemical calculation) was performed.

Figure 31 is based on the unrestricted Hartree-Fock method (UHF) / 6-31G * using a model in which one molecule of the radical species TTF ^{· +} COO · NH ₄ is embedded in a tetramer of TTFCOO · NH ₄ salt. It is a figure which shows an electronic state. In the figure, a) pseudo-closed shell configuration, b) molecular orbital diagram. In both results, it was found that the single occupied molecular orbital (SOMO) of radical species is not in the frontier orbital, but is localized in a more stabilized orbital. This pseudo-closed-shell configuration is expressed for a compound having a form in which radical species are embedded in a supramolecular arrangement utilizing hydrogen bonding.

Examples of acceptor molecules that are considered to exhibit similar effects are listed below.

FIG. 32 is a diagram showing the results of periodic quantum chemical calculations performed for a cluster model including one radical species in four molecular units in consideration of the periodicity in the hydrogen bonding direction (one-dimensional). The band gap at the M point is only 0.3 eV, and it reproduces semiconductor properties well. This confirms that conduction carriers are generated by splitting the orbit near SOMO due to the pseudo-closed shell arrangement. The calculation method was as follows.
Periodic Boundary Condition (PBC) -UHF / 3-21G *
Brillian zone sampling: 40k x 1 x 1 point calculation program: Gaussian03, Rev. D 01
[Negative magnetoresistance effect]

The group of substances described in this specification, such as the above-mentioned chemical formula 1 to chemical formula 11, is an organic substance doped to compensate for the loss charge of proton defects generated in the salt bridge bond. These substance groups produce a negative magnetoresistive effect corresponding to the applied magnetic field in either a powder molded pellet or single crystal state.

Hereinafter, various materials will be described with specific examples.

Table 2 shows crystallization solvent dependence of magnetoresistance of TTFCOO ^- NH ₄ ⁺ salt (300K), that is, powder molding by changing the amount of dope by recrystallizing TTFCOO ^- NH ₄ ⁺ salt from various solvents by recrystallization. The excitation current value of the pellet sample and the magnitude of negative magnetoresistance (MR) at room temperature when 9T is applied. In both cases, an MR effect in the range of 0.35-0.55% is confirmed.

Table 3 shows the increase in magnetic resistance (300K) due to ammonia treatment of TTFCOO ^- NH ₄ ⁺ salt, that is, the data when the powder crystal precipitated from diethyl ether was left in an ammonia gas atmosphere for 1 minute. Indicates. In this case, an MR effect increase of about 30% is confirmed compared to the state before ammonia treatment.

Table 4 shows the magnetoresistance characteristics (300K) of a single crystal sample of TTFCOO ^- NH ₄ ⁺ salt, that is, the MR effect when 9T is applied to a single crystal of the same substance.

FIG. 33 shows the external magnetic field dependence at 300K of powder-molded pellet samples of the same material. As an example, the value of a sample precipitated from a tetrahydrofuran (THF) solvent is shown. A substantially linear negative magnetoresistance effect is generated according to the applied magnetic field.

Table 5 shows the magnetoresistance effect of the TTFCOO ^- NH ₃ ⁺ OH salt single crystal sample, that is, the MR effect of 300K and 130K when 9T is applied to the TTFCOO ^- NH ₃ ⁺ OH salt single crystal.

FIG. 34 shows the magnetic field dependence of MR at 300 K for the same material.

FIG. 35 shows the temperature dependence of the MR effect of the same substance at 9T. The magnetoresistive effect increases substantially linearly at lower temperatures. For example, the magnetoresistance effect increases in the temperature range of 250K-300K, 200K-300K, and 130K-300K.

Table 6, TTFCOO ^- NH ₃ ⁺ Ph single crystal magneto-resistance effect of salt (300K), i.e., TTFCOO ^- shows the 300K of the MR effect during 9T application of NH ₃ ⁺ Ph salts single crystal.

FIG. 36 shows the magnetic field dependence of MR of the same substance at 300K.

FIG. 37 shows the temperature dependence of the MR effect of the same substance at 9T.

FIG. 38 shows the magnetic field dependence of the MR effect at 300 K of DBTTF (CH) (CH ₃ ) NH ₃ .Br salt.

All materials showed an MR effect of 1% or less near room temperature, indicating that the self-doped electronic state has carriers that respond to a magnetic field. The origin of this phenomenon is caused by the interaction between the ferromagnetic spin component of the substance group and the conduction carrier, and proves the existence of the ferromagnetic spin component of the substance group.

The group of substances described in the present specification such as Chemical Formula 1 to Chemical Formula 11 described above are organic semiconductors containing ammonium ions as a main skeleton, and when proton defects of 0.1% or more and 99.9% or less are generated on ammonium ions, It has been revealed that conductivity is greatly expressed. As described above, in an organic semiconductor in which proton defects on ammonium serve as a dopant, magnetism occurs around the dopant, so that charge carriers are affected by the influence and develop a negative magnetoresistance when a magnetic field is applied. The effect of the generation of ferromagnetism around the defect structure is the first case of the substance group described in this specification in the organic matter, so it is inevitable that the substance development will be greatly affected in the future. The ferromagnetism generated in the salt bridge structure including proton defects is observed not only at low temperatures but also at high temperatures such as room temperature, and all cases show that they are not easily affected by temperature. Therefore, all substances that generate charge carriers with this dopant exhibit a negative magnetoresistance effect.

[Synthesis method]

Next, a specific method for synthesizing the compound will be described.

(Synthesis of tetrathiafulvalene-2-carboxylic acid)

Dry diethyl ether (10 ml) was added to diisopropylamine (0.65 ml, 5.42 mmol) under an argon atmosphere, and n-BuLi (1.65 mol / L, 5.45 mmol) was slowly added dropwise. This was stirred for 1 hour on an ice bath to prepare lithium diisopropylamide (LDA). Under an argon atmosphere, tetrathiafulvalene (TTF) (1.014 g, 4.96 mmol) was dissolved in dry diethyl ether (100 ml), and the prepared LDA was slowly added dropwise using a cannula while stirring at -78 ° C. The mixture was stirred for 15 minutes while maintaining the temperature, and precipitation of the lithio compound was confirmed. Dry ice passed through dry diethyl ether was added thereto, and the temperature was returned to room temperature overnight. A solid was obtained by filtration and then washed with diethyl ether. The obtained solid was dissolved in alkaline water, and the aqueous layer was washed with diethyl ether. The aqueous layer was acidified with 3M HCl and extracted with diethyl ether. The diethyl ether layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain red solid tetrathiafulvalene-2-carboxylic acid (0.8023 g, 3.23 mmol, 65%).
¹ H NMR (DMSO): δ = 7.67 (s, 1H), 6.75 (s, 2H) ppm.
IR (KBr): 3060, 2930, 1650, 1530, 1420, 1290 cm ^-1 .

(Preparation of tetrathiafulvalene-2-carboxylic acid / ammonium salt)

Tetrathiafulvalene-2-carboxylic acid (150 mg, 0.604 mmol) was dissolved in dry diethyl ether (30 ml), and insoluble components were removed by suction filtration. A 28% aqueous ammonia solution was dropped into the filtrate, and a solid was deposited on an ultrasonic generator over 15 seconds. The precipitated solid was filtered, washed with diethyl ether, stirred while suspended in toluene (3 ml), and then filtered to obtain tetrathiafulvalene-2-carboxylic acid / ammonium salt (130.8 mg, 0.493 mmol, 82%).
¹ H NMR (DMSO): δ = 6.75 (s, 2H), 7.67 (s, 1H) ppm.
IR (KBr): 2930, 1650, 1530, 1420, 1290 cm ^-1 .
Anal.Calcd.for C ₇ H ₆ N O ₂ S ₄ : C, 31.68; H, 2.66; N, 5.28. Found. C, 31.59; H, 2.75; N, 5.10.

(Synthesis of 1- (dibenzotetrathiafulvalen-2-yl) ethylamine)

<1,3-Benzodithiol-2-thione>
To a 100 ml flask purged with argon was added isoamyl alcohol (0.80 ml, 0.73 mmol), carbon disulfide (4.0 ml, 6.6 mmol), 1,2-dichloroethane (20 ml), isoamyl nitrile (0.97 ml, 0.73 mmol), Anthranilic acid (1.00 g, 7.30 mmol) dissolved in 1,4-dioxane (4 ml) was added with heating and stirring. After heating at reflux for 10 hours, the reaction was stopped by adding water, 3M aqueous potassium hydroxide solution was added, extracted with dichloromethane, dried and concentrated to obtain 1.29 g of a brown liquid. Subsequently, the origin component was removed by silica gel column chromatography. To this, sulfur (0.143 g, 4.46 mmol) and orthodichlorobenzene (2.0 ml) were added and heated to reflux for 4 hours. This was allowed to stand overnight, and the resulting crystals were filtered to obtain 1,3-benzodithiol-2-thione (0.383 g, 2.08 mmol, 51%) as brown needle crystals.
¹ H NMR (CDCl ₃ ): δ = 7.26-7.42 (m, 2H), 7.46-7.50 (m, 2H) ppm.
IR (KBr): 1434, 1264, 1119, 1059, 1025, 741, 474, 892 cm ^-1 .

<4,5-dimethyl-1,3-dithiol-2-one>
Under argon atmosphere, a solution of distilled and purified ethyl methyl ketone (0.53 mg, 5.9 mmol) in acetonitrile (8 ml) was added to a 30 ml flask and stirred at room temperature with bromotetramethylsilane (0.86 ml, 6.2 mmol) and distilled and purified dimethyl sulfoxide (0.46 ml, 6.5 mmol) were added, and the mixture was stirred on an ice bath for 1 hour. To this was added potassium isopropylxanthate (1.14 g, 6.53 mmol), and the mixture was further stirred at room temperature for 1 hour. The reaction was stopped by adding water, 1M hydrochloric acid was added, extracted with diethyl ether, dried and concentrated. The concentrate was dissolved in a chloroform / ether (1: 1) solution (8 ml), and a 60% aqueous solution of perchloric acid (2 ml) was added dropwise with stirring in a 50 ml flask. . The reaction was stopped by adding water, extracted with diethyl ether, dried and concentrated. The resulting solid was purified by silica gel column chromatography (hexane → hexane / dichloromethane (3: 1)) to give colorless crystals of 4,5-dimethyl-1,3-dithiol-2-one (0.37 g, 2.5 mmol, 43%).
¹ H NMR (CDCl ₃ ): δ = 2.15 (s, 6H) ppm.
IR (KBr): 1655, 1600, 1438, 1188, 1092, 885, 755, 418 cm ^-1 .

<5-acetyl-1,3-benzodithiol-2-one>
Under an argon atmosphere, a solution of 4,5-dimethyl-1,3-dithiol-2-one (0.445 g, 3.04 mmol) in carbon tetrachloride (18 ml) was added to a 50 ml flask and stirred. Bromosuccinimide (NBS) (2.38 g, 13.4 mmol) was added. The mixture was heated to reflux for 10 hours under incandescent bulb irradiation, and then stirred at room temperature for 13.5 hours. The reaction solution was filtered, and the filtrate was concentrated to dryness and dried to obtain 1.26 g of a black solid (crude yield 107%). The resulting black solid and tetrabutylammonium iodide (2.34 g, 9.09 mmol) were added to a 50 ml flask, dissolved in acetonitrile (14 ml) and heated to reflux for 5 hours, where methyl vinyl ketone (1.93 ml, 12.7 mmol) was added dropwise, followed by heating to reflux for 30 minutes. After concentration, the obtained solid was purified by silica gel column chromatography (dichloromethane / hexane (1: 1) → (4: 3)) to give 5-acetyl-1,3-benzodithiol-2-one (0.222 g, 1.06 mmol, 39%).
¹ H NMR (CDCl ₃ ): δ = 2.63 (s, 3H), 7.60 (d, 1H, J = 4.2 Hz), 7.90 (dd, 1H, J = 1.7 Hz, J = 3.3 Hz), 8.09 (d, 1H, J = 1.2 Hz) ppm.
IR (KBr): 3078, 2923, 1687, 1638, 1391, 1355, 1273, 1248, 889, 818 cm ^-1 .

<5- (2-Methyl-1,3-dioxalan-2-yl) -1,3-benzodithiol-2-one>
Add a solution of 5-acetyl-1,3-benzodithiol-2-one (0.222 g, 1.06 mmol) in toluene (12 ml) to a 50 ml flask purged with argon, and stir it. Paratoluenesulfonic acid monohydrate (0.059 g, 0.34 mmol) was added, ethylene glycol (0.3 ml) was further added, and the mixture was heated to reflux for 4 hours. Thereafter, about 1.5 ml of triethylamine was added to stop the reaction, and the mixture was further stirred at room temperature for 1 hour. The reaction solution was concentrated and dried to obtain 0.359 g of a brown oil. This was purified by silica gel column chromatography (dichloromethane / hexane (2: 1) → dichloromethane only) to give 5- (2-methyl-1,3-dioxalan-2-yl) -1,3-benzodithiol-2- On (0.158 g, 0.621 mmol, 59%) was obtained.
¹ H NMR (CDCl ₃ ): δ = 1.66 (s, 3H), 3.76-3.81 (m, 2H), 4.04-4.09 (m, 2H), 7.45 (s, 2H), 7.63 (s, 1H) ppm.
IR (KBr): 3421, 1685, 1638, 1375, 1274, 1243, 1195, 1038, 878 cm ^-1 .

<2-acetyldibenzotetrathiafulvalene>
1,3-benzodithiol-2-thione (1.19 g, 6.46 mmol) and 5- (2-methyl-1,3-dioxalan-2-yl) -1,3-benzodithiol-2-one (0.66 g, 2.60 mmol) and triethyl phosphite (70 ml) were added to a 200 ml flask purged with argon, and the mixture was heated to reflux for 9 hours. Water was added, 3M hydrochloric acid was added dropwise while cooling in an ice bath, and the mixture was concentrated and dried. The product was purified by silica gel column chromatography (chloroform only → ethyl acetate only) and recrystallized from chloroform to obtain 2-acetyldibenzotetrathiafulvalene (0.481 g, 1.39 mmol, 53%).
¹ H NMR (CDCl ₃ ): δ = 2.57 (s, 3H), 7.12-7.15 (m, 2H), 7.26-7.33 (m, 2H), 7.69 (dd, 2H, J = 3.5 Hz, J = 0.6 Hz ), 7.83 (d, 1H, J = 0.8 Hz) ppm.
IR (KBr): 1668, 1568, 1447, 1390, 1348, 1272, 1235, 1121, 810, 748 cm ^-1 .

<O-methyl-2-acetyldibenzotetrathiafulvalene oxime>
Add 2-acetyldibenzotetrathiafulvalene (0.98 g, 2.83 mmol) to a 200 ml flask, add pyridine (70 ml) and stir, and add O-methylhydroxyamine hydrochloride (0.354, 4.24 mmol) here. The mixture was heated to reflux for 6 hours and stirred at room temperature for 40 hours. Water was added to the reaction mixture, and the mixture was extracted with dichloromethane. The organic layer was concentrated and dried. The product was recrystallized from chloroform, and O-methyl-2-acetyldibenzotetrathiafulvalene oxime (0.85 g, 2.26 mmol, 80% )
¹ H NMR (CDCl ₃ ): δ = 2.17 (d, 3H, E / Z mixture), 3.98 (d, 3H, E / Z mixture), 7.10-7.13 (m, 2H), 7.21-7.27 (m, 5H ), 7.38 (d, 1H, J = 4.2 Hz), 7.58 (d, 1H, E / Z mixture) ppm.
IR (KBr): 3436, 2923, 1653, 1444, 1050, 892, 818, 745 cm ^-1 .

<1- (Dibenzotetrathiafulvalen-2-yl) ethylamine>
To a 300 ml flask purged with argon, add O-methyl-2-acetyldibenzotetrathiafulvalene oxime (1.92 g, 5.12 mmol) and THF (160 ml) and stir. Under ice cooling, borane tetrahydrofuran complex tetrahydrofuran solution (21.1 ml, 21.4 mmol) was added and heated to reflux for 3 hours. 1M hydrochloric acid (20 ml) was added to the cooled reaction solution to stop the reaction, and an aqueous potassium hydroxide solution was added little by little and concentrated to remove THF to some extent, and then the solution was made basic and extracted with dichloromethane. The organic layer was concentrated and dried to give 1- (dibenzotetrathiafulvalen-2-yl) -ethylamine (1.67 g, 4.79 mmol, 94%).
¹ H NMR (CDCl ₃ ): δ = 1.35 (d, 3H, J = 3.3 Hz), 4.08 (q, 1H, J = 3.3 Hz), 7.08-7.14 (m, 3H), 7.19-7.29 (m, 4H ) ppm.
IR (KBr): 3046, 2922, 1561, 1445, 1428, 1260, 1120, 1028, 811, 776, 737 cm ^-1 .

(Preparation of Bronsted acid salt)

For salts with various acids, 1- (dibenzotetrathiafulvalen-2-yl) ethylamine is dissolved in a solvent (diethyl ether or dichloromethane), and a Bronsted acid aqueous solution (HBr, HBF ₄ ) is added dropwise thereto for several minutes. It was prepared by applying ultrasonic waves and filtering the resulting solid. Distilled water used for one washing was washed by performing a few drops with a Pasteur pipette about 5 times.

<1- (Dibenzotetrathiafulvalen-2-yl) ethylamine / bromate>
¹ H NMR (DMSO-d6): δ = 1.49 (d, 3H, J = 6.9 Hz), 4.40 (s, 1H), 7.27-7.76 (m, 7H), 8.21 (s, 3H) ppm.
IR (KBr): 2923, 1590, 1497, 1444, 1222, 1080, 738, 591, 435 cm ^-1 .
Anal.Calcd.for C ₁₆ H ₁₄ BrNS ₄・ H ₂ O: C, 43.03%; H, 3.62%; N, 3.14%. Found. C, 43.24%; H, 3.37%, N, 3.04%.

<1- (Dibenzotetrathiafulvalen-2-yl) ethylamine tetrafluoroborate>
¹ H NMR (DMSO-d6): δ = 1.50 (d, 3H, J = 6.9 Hz), 4.39 (q, 1H, J = 6.9 Hz), 7.33 (m, 4H), 7.62 (m, 5H) ppm.
IR (KBr): 2924, 1616, 1498, 1445, 1225, 1083, 741, 591, 523, 415 cm ^-1 .
Anal.Calcd.for C ₁₆ H ₁₄ B F ₄ N S ₄ : C, 44.14%; H, 3.24%; N, 3.22%. Found. C, 43.96%; H, 3.40%, N, 3.17%.

[Ingenuity in the synthesis process]

Increasing the radical spin concentration in the solid by carrier doping is an important factor in improving the magnetic properties, but by changing the crystallization solvent, the spin concentration can be up to 38% (using 1,4-dioxane). Succeeded in improving.

FIG. 11 is a diagram showing the correlation between the solvent used for crystallization of ammonium salt and the spin concentration of the obtained carrier-doped crystal. *

The experiment was carried out by ESR measurement of pellet-shaped small pieces of carrier-doped salt polycrystals at room temperature, and the ESR signal was measured using the standard 2,2-diphenyl-1-picrylhydrazyl ( The spins were quantified in comparison with the peak area of 2,2-diphenyl -1-picrylhydrazyl) (commonly called DPPH). All sample quantities used are standardized.

[Usage]

The compound of this embodiment can be used for various uses. Spintronics device, information communication device, memory device, magnetic shield, medical magnetic shield, magnet, magnetic semiconductor, field effect transistor (FET), adhesive bandage, hard disk drive head, high-sensitivity playback GMR head, solid-state magnetic memory, Examples include magnetoresistive memory (MRAM), optical isolators for fiber communication, materials that change color with a magnetic field, and materials that use the interaction between conduction electron spin and atomic magnetic moment.

In addition, even if it is not a single crystal, it shows a high physical property value in the microcrystalline pressure molding state, suggesting the possibility that it can be converted into a polymer or liquid crystal and thinned. Thin film formation by coating opens up possibilities for many applications.

[Interpretation of rights, etc.]

The present invention has been described above with reference to specific embodiments. However, it is obvious that those skilled in the art can make modifications or substitutions of the embodiments without departing from the gist of the present invention. That is, the present invention has been disclosed in the form of exemplification, and the contents described in the present specification should not be interpreted in a limited manner. In order to determine the gist of the present invention, the claims section described at the beginning should be considered.

It will also be appreciated that illustrative embodiments of the invention achieve the above objects, but that many modifications and other examples can be made by those skilled in the art. The elements or components of each embodiment described in the claims, specification, drawings, and description may be employed in combination with one or more other elements. The claims are intended to cover such modifications and other embodiments, which are within the spirit and scope of the present invention.

Claims (33)

1. Formed by salting organic molecules that serve as donors with inorganic acids or bases,
   An organic itinerant magnetic compound characterized by self-assembly.
2. 2. The organic itinerant magnetic compound according to claim 1, which has an ammonium moiety.
3. 3. The organic itinerant magnetic compound according to claim 2, wherein hydrogen bonds are made to the ammonium moiety in a self-assembled state.
4. An organic itinerant magnetic compound, characterized in that it is formed by inducing a compound containing a tetrathiafulvalene analog moiety in the skeleton and having a protonic acid functional group into a salt with ammonia or a salt with hydroxyamine.
5. An organic itinerant magnetic compound formed by inducing a compound having a tetrathiafulvalene analog moiety in a skeleton and having a primary amine into an inorganic acid salt.
6. An organic itinerant magnetic compound, which is any compound represented by the formula (1):
   

   

   (X ⁴ wherein the X ¹ is S or Se, R ¹ is any one expressed in the formula 2.) (One wherein, R ⁸ from R ² is represented in (formula 3) (It may be the same or different.)
   

   

   
7. An organic itinerant magnetic compound, which is any compound represented by the formula (4):
   

   
8. An organic itinerant magnetic compound, which is any compound represented by the formula (5):
   

   
9. An organic itinerant magnetic compound characterized by being tetrathiafulvalene-2-carboxylic acid / ammonium salt.
10. A method for producing an organic itinerant magnetic compound, characterized in that an organic molecule serving as a donor is formed by salt formation with an inorganic acid or an inorganic base on a one-to-one basis to produce a self-assembling compound.
11. An organic itinerant magnetic compound characterized by having a pseudo-closed shell configuration.
12. Including salt bridge bonds,
    An organic itinerant magnetic compound formed by adding a Brönsted acid or base to an organic compound having a molecular weight of 20000 or less and stably generating 0.1% or more radical species.
13. A salt bridge material having multiple bonds that can be protonated in an electron donor molecule or in an electron acceptor molecule;
    An organic itinerant magnetic compound formed by the stable generation of 0.1% or more of the radical species during salt bridge formation.
14. A salt bridge substance having a tetrathiafulvalene skeleton or a tetraselenafulvalene skeleton,
    An organic itinerant magnetic compound formed by the stable generation of 0.1% or more of the radical species during salt bridge formation.
15. 15. The organic itinerant magnetic compound according to claim 13, wherein the electronic state of the radical spin has a pseudo-closed shell configuration.
16. A method for producing an organic itinerant magnetic compound containing a salt bridge bond,
    A method for producing an organic itinerant magnetic compound formed by adding a Bronsted acid or a base to an organic compound having a molecular weight of 20000 or less and stably generating at least 0.1% of radical species.
17. A method for producing an organic itinerant magnetic compound which is a salt bridge substance having multiple bonds that can be protonated in an electron donor molecule or an electron acceptor molecule,
    A method for producing an organic itinerant magnetic compound formed by stably generating at least 0.1% of radical species in the formation of a salt bridge.
18. A method for producing an organic itinerant magnetic compound which is a salt bridge substance having a tetrathiafulvalene skeleton or a tetraselenafulvalene skeleton,
    A method for producing an organic itinerant magnetic compound formed by stably generating at least 0.1% of radical species in the formation of a salt bridge.
19. 19. The method for producing an organic itinerant magnetic compound according to claim 17, wherein the electronic state of the radical spin has a quasi-closed shell configuration.
20. 10. The organic itinerant magnetic compound according to claim 9, which is a semiconductor.
21. 10. The organic itinerant magnetic compound according to claim 9, wherein the organic itinerant magnetic compound is a ferromagnetic material.
22. 10. The organic itinerant magnetic compound according to claim 9, which is an organic room temperature itinerant magnetic compound.
23. 10. A magnet containing the organic itinerant magnetic compound according to claim 9.
24. 10. A spintronic device comprising the organic itinerant magnetic compound according to claim 9.
25. A hydrogen purification material containing the organic itinerant magnetic compound according to claim 9.
26. Organic organic compound containing a proton defect in a salt bridge bond and generating a radical cation or radical anion to compensate for the lost charge.
27. An organic itinerant magnetic compound that generates radical cations or radical anions to compensate for lost charges due to the abundance ratio of cation and anion deviating from 1: 1 in the salt bridge material.
28. 2. The organic itinerant magnetic compound according to claim 1, which produces a negative magnetoresistance effect.
29. 7. The organic itinerant magnetic compound according to claim 6, which produces a negative magnetoresistance effect.
30. 10. The organic itinerant magnetic compound according to claim 9, which produces a negative magnetoresistance effect.
31. 10. The organic itinerant magnetic compound according to claim 9, which produces a substantially linear negative magnetoresistance effect in accordance with an applied magnetic field.
32. 32. The organic itinerant magnetic compound according to claim 31, wherein the magnetoresistive effect increases as the temperature decreases.
33. 32. The organic itinerant magnetic compound according to claim 31, wherein the magnetoresistive effect increases as the temperature becomes lower in a temperature range of 250K to 300K.

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