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Tetracyanoquinodimethane rare earth complex and synthetic method and application thereof

A technology of benzoquinodimethane and rare earth complexes, which is applied in the field of tetracyano-p-benzoquinodimethane TCNQ rare earth complexes and their synthesis, and can solve the problems of rare rare earth metals and the like

Inactive Publication Date: 2010-07-28
HEILONGJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In recent years, a large number of TCNX metal complex molecular magnetic materials have been synthesized, but these works mainly focus on transition metals, and there are few rare earth metals.

Method used

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  • Tetracyanoquinodimethane rare earth complex and synthetic method and application thereof
  • Tetracyanoquinodimethane rare earth complex and synthetic method and application thereof
  • Tetracyanoquinodimethane rare earth complex and synthetic method and application thereof

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Experimental program
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Embodiment 1

[0030] Synthesis and Structure of TCNQ Rare Earth Complex Ln(TCNQ)

[0031] In the following reaction equation, LnCl3·nH2O and Li(TCNQ) are the reaction raw materials, methanol, ethanol and water are the reaction solvents, and Ln(TCNQ) is the reaction product. Under the protection of nitrogen, in the Schlenk tube, add the deoxygenated methanol solution or deoxyethanol solution of LnCl3 nH2O dropwise along the wall of the Schlenk tube to the upper layer of the deoxygenated double-distilled aqueous solution of LiTCNQ, seal and place the Schlenk tube, TCNQ rare earth complex Ln(TCNQ) was synthesized by slow heterogeneous solution diffusion reaction of LnCl3·nH2O deoxygenated methanol solution or deoxyethanol solution to deoxygenated double-distilled aqueous solution of LiTCNQ.

[0032] The synthetic method of described tetracyano-p-benzoquinone dimethane rare earth complex, described Ln is La lanthanum, Ce cerium, Pr praseodymium, Nd neodymium, Sm samarium, Eu europium, Gd gadoli...

Embodiment 2

[0035] Structure of TCNQ Rare Earth Complex Ln(TCNQ)

[0036] Single crystal X-ray diffraction analysis shows that Ln(TCNQ) is an ion-pair compound with two types of molecular structures, one is zero-dimensional dimeric molecular structure, and the other is zero-dimensional mononuclear molecular structure. attached figure 1 And attached figure 2 Two representative molecular structures of Ln(TCNQ) are given respectively.

Embodiment 3

[0038] Molecular Magnetic Properties of TCNQ Rare Earth Complex Ln(TCNQ)

[0039] The DC magnetization curve of La(TCNQ) (attached image 3 ) shows that the π-π antiferromagnetic interaction between TCNQ radical anions exists in the series of complexes Ln(TCNQ). DC magnetization curves of Pr(TCNQ), Dy(TCNQ) and Er(TCNQ) with variable temperature (attached Figure 4 ) shows that the molecular magnetism of the three complexes is similar, that is, as the temperature decreases, the thermal extinction of the Stark (Stark) energy level of the trivalent rare earth ion in the complex and the π-π reaction between the TCNQ radical anions Together, the ferromagnetic interactions lead to a decrease in the x mT value.

[0040] The molecular magnetic properties of Gd(TCNQ) changed obviously before and after the solvent molecules were removed in vacuum at high temperature. attached Figure 5 It shows that before Gd(TCNQ) is desolvated, there is antiferromagnetic interaction between the s...

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Abstract

The invention discloses a tetracyanoquinodimethane rare earth complex and a synthetic method and application thereof. The tetracyanoquinodimethane rare earth complex Ln(TCNQ) is synthesized and structurally characterized by adopting standard Schlenk technology, taking LnCl3.nH20 and LiTCNQ as raw materials, taking deoxidized methanol, ethanol and double-distilled water as solvents through slow heterogeneous solution diffusion reaction. The complex has two molecular structures, namely, zero-dimension dimeric molecular structure and zero-dimension mononuclear molecular structure. The complex and a compound thereof of which the solution is removed have good molecular magnetism. The complex and the method of the invention have wide application prospect which includes the application in the technical field of preparation of magnetic materials.

Description

Technical field: [0001] The invention relates to a tetracyanoquinone dimethane TCNQ rare earth complex and a synthesis method and application thereof. Background technique: [0002] TCNQ (tetracyanoquinone dimethane), TCNE (tetracyanoethylene), TCNB (1,2,4,5-tetracyanobenzene) and TCNP (2,3,5,6-tetracyanopyridine The free radical anions of organic polycyanides such as azine) are an important class of organic free radical spin carriers, which can produce localized superexchange interactions with paramagnetic metal ions through spin coupling. This magnetic interaction is the formation of Necessary for molecular magnetic materials. [0003] In recent years, a large number of TCNX metal complex molecular magnetic materials have been synthesized, but these works mainly focus on transition metals, and there are few rare earth metals. A large number of spins and strong spin-orbit coupling lead to trivalent rare earth ions generally have a large anisotropic magnetic moment, so tri...

Claims

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Application Information

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IPC IPC(8): C07F5/00C07C255/31H01F1/42
Inventor 李光明闫鹏飞张巨文孙文彬李洪峰许辉
Owner HEILONGJIANG UNIV
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