CN111171074B - Benzyl triphenyl phosphine tetranuclear manganese (II) complex - Google Patents

Benzyl triphenyl phosphine tetranuclear manganese (II) complex Download PDF

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CN111171074B
CN111171074B CN202010110048.3A CN202010110048A CN111171074B CN 111171074 B CN111171074 B CN 111171074B CN 202010110048 A CN202010110048 A CN 202010110048A CN 111171074 B CN111171074 B CN 111171074B
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complex
chloride
room temperature
benzyltriphenylphosphonium
stirring
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CN111171074A (en
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谭育慧
李玉孔
杨康
董杏娴
宋宁
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Jiangxi University of Science and Technology
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    • C07ORGANIC CHEMISTRY
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    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/54Quaternary phosphonium compounds
    • C07F9/5442Aromatic phosphonium compounds (P-C aromatic linkage)
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Abstract

The invention discloses a benzyltriphenylphosphonium tetranuclear manganese (II) complex, which has the molecular formula as follows:
Figure DDA0002389674870000011
the invention synthesizes the hybrid material at room temperature by taking metal chloride, benzyltriphenylphosphonium chloride and potassium thiocyanate as raw materials, and the material has excellent fluorescence property and important value in nonlinear optical property and information storage aspect.

Description

Benzyl triphenyl phosphine tetranuclear manganese (II) complex
Technical Field
The invention relates to the field of materials, in particular to a benzyltriphenylphosphonium tetranuclear manganese (II) complex, application thereof as a fluorescent material and a preparation method thereof.
Background
The preparation of molecular materials with special structure, optics, conductivity and magnetism using crystal engineering and supramolecular chemistry has attracted considerable interest, with some non-covalent interactions such as weak P.junction interaction or Pi.junction interaction and H-bond interaction being used to obtain some new materials, with wide applications in the field of photovoltaics.
The development trend and direction of the current inorganic chemistry have the characteristics of scientifically combining with materials, compounding, assembling and hybridizing inorganic functional materials by applying molecular design and molecular engineering ideas, strengthening the relationship between the structure and the performance of functional substances and the like. Since these materials are composed of inorganic phase, the structural modification and modification are difficult, and it is difficult to control the size, shape and physicochemical properties according to actual needs. While organic compounds have excellent molecular tailoring and modification functions, they have significant drawbacks in terms of robustness and stability. How to combine the complementary properties of inorganic and organic compounds, and constructing a novel hybrid material with a plastic, stable and firm structure has become an important research topic in the fields of inorganic chemistry and material science. In recent years, the research on the synthesis of Mn (II) -based coordination compounds has attracted considerable attention due to their interesting molecular topology and their great potential for applications in catalysis, magnetism and fluorescence properties.
Disclosure of Invention
The invention aims to provide a novel nonlinear optical material and a synthetic method thereof. In order to realize the purpose of the invention, the following technical scheme is adopted:
one of the objects of the present invention is to provide benzyltriphenylphosphonium tetranuclear manganese (ii) complexes of the formula:
Figure BDA0002389674850000021
the heterocyclic organic ligand in the molecular structural formula is benzyltriphenylphosphonium chloride, SCN is thiocyanate, and Mn is metal manganese ions.
In a preferred embodiment of the present invention, the complex is a particulate crystal; preferably, the granular crystals are pink granular crystals.
The invention also relates to the application of the benzyltriphenylphosphonium tetranuclear manganese (II) complex as a fluorescent material and/or a nonlinear optical material.
The invention also relates to a preparation method of the benzyltriphenylphosphonium tetranuclear manganese (II) complex, which is characterized by comprising the following steps:
A. adding metal Mn chloride, thiocyanate and methanol into a container, stirring at room temperature, adding benzyltriphenylphosphonium chloride into the solution, continuously stirring, and filtering to obtain a clear solution;
B. evaporating the obtained clear liquid at room temperature for 4-6 days to obtain the target product.
The synthetic route of the preparation method of the invention is as follows:
Figure BDA0002389674850000022
in a preferred embodiment of the invention, the stirring is carried out at room temperature for a period of 30 to 60 minutes
In a preferred embodiment of the invention, benzyltriphenylphosphonium chloride is added to the solution for an additional stirring time of 20 to 60 minutes.
In a preferred embodiment of the invention, it is characterized in that the molar ratio of the metal Mn chloride, thiocyanate and methanol is between 2 and 4.
The invention synthesizes the hybrid material at room temperature by taking metal chloride, benzyltriphenylphosphonium chloride and potassium thiocyanate as raw materials, and the material has excellent fluorescence property and important value in nonlinear optical property and information storage aspect.
Drawings
FIG. 1: example 1 [ BPP ] prepared 2 [Mn(NCS) 4 ]A crystal photograph of the material (the photograph was taken with a camera and the crystal size was about 3x 2.5x2mm).
FIG. 2 is a schematic diagram: powder X-ray diffraction pattern of the complex prepared in example 1.
FIG. 3: solid state fluorescence spectrum of the complex prepared in example 1.
FIG. 4 is a schematic view of: second order nonlinear optical effects of the complex prepared in example 1.
Detailed Description
The invention is further described in the following detailed description in conjunction with specific examples, which are intended to be illustrative, but not limiting, of the invention, and the methods and reagents used in the invention, as well as other alternatives and alternatives, which achieve the same technical result.
Example 1:
A. dissolving 0.198 g of manganese chloride solid and 0.389 g of thiocyanate solid in 5ml of methanol at a certain temperature (room temperature), and stirring for half an hour to obtain a clear solution A;
B. weighing 0.777 g of benzyltriphenylphosphonium chloride solid at room temperature, and dissolving in 10ml of methanol solution to obtain colorless clear solution B;
C. adding the solution B into the solution A, continuously stirring for half an hour to obtain a turbid liquid, filtering with medium-speed filter paper, standing the obtained supernatant at room temperature for 3-4 days, slowly evaporating to obtain pink granular crystals (shown in figure 1), which are the target products of the hybrid material (the target product is a single pure phase through single crystal X-ray diffraction and powder X-ray diffraction, shown in figure 2.)
At room temperature, the solid state fluorescence properties of the complexes were tested and analyzed (solid state fluorescence test on F-4600 type fluorescence spectrometer (Hitachi, japan), selecting a small number of samples to be tested on a quartz glass slide, for samples of unknown excitation wavelength, first selecting an excitation wavelength, then performing a full-band scan, taking the maximum value in the scanned emission spectrum, the maximum excitation peak of the complex being 248nm, and then measuring the emission peak at this excitation peak state.) FIG. 3 shows the ultraviolet spectrum between 340nm and 470nm, the results of exciting the complex at 248nm showing that [ (BPP) 2 Mn(NCS) 4 ]A strong emission band at 396nm is generated and the size of the peak is attributed to the Mn within the ligand 2+ Pi-pi transition of (c). Therefore, the complex can be used as a purple luminescent material.
This prompted the inventors to study their nonlinear optical properties, since the complexes have a non-centrosymmetric space group Cc. The second-order nonlinear optical effect of the complex is shown in fig. 4 (calibrating with potassium dihydrogen phosphate (KDP) on a nonlinear optical testing instrument, testing the complex, collecting data and processing the data), and the complex has strong SHG response (about 2 × KDP (KH)) through testing 2 PO 4 )). Therefore, the complex can be used as a second-order nonlinear optical material.
The above detailed description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention. While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. A complex of the formula:
Figure FDA0003794001140000011
2. the complex of claim 1, which is a particulate crystal.
3. The complex of claim 2, the particulate crystals being pink particulate crystals.
4. Use of a complex according to any one of claims 1 to 3 as a fluorescent material and/or a nonlinear optical material.
5. A process for preparing a complex as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
A. adding metal Mn chloride, thiocyanate and methanol into a container, stirring at room temperature, adding benzyltriphenylphosphonium chloride into the solution, continuously stirring, and filtering to obtain a clear solution;
B. evaporating the obtained clear liquid at room temperature for 4-6 days to obtain the target product.
6. The method according to claim 5, wherein the stirring time at room temperature is 30 to 60 minutes.
7. The method of claim 5, wherein the benzyltriphenylphosphonium chloride is added to the solution and the stirring is continued for 20 to 60 minutes.
8. The process according to claim 5, wherein the molar ratio of the metal Mn chloride, thiocyanate and methanol is from 2 to 4.
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Citations (1)

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US5512407A (en) * 1994-12-07 1996-04-30 Eastman Kodak Company Bis(quaternary phosphonium) tetrahalomanganate salts as charge-control agents

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5512407A (en) * 1994-12-07 1996-04-30 Eastman Kodak Company Bis(quaternary phosphonium) tetrahalomanganate salts as charge-control agents

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LI Yu-Kong等.Syntheses, Crystal Structures, SHG Response and Purple Luminescent Property of Tetra(isothiocyanate) Mn(II) and Substituted Benzyl Triphenylphosphonium Cations.《Chinese J.Struct.Chem.》.2021,第40卷(第6期),第739-745页. *
Qiang Li等.A Switchable Molecular Dielectric with Two Sequential Reversible Phase Transitions:[(CH3)4P]4[Mn(SCN)6].《Inorg.Chem.》.2015,第54卷第10642-10647页. *
沈昊宇 等.一个含铜(II)四氮大环阳离子和锰(II)一维链阴离子化合物{[Cu(trans[14]diene)SCN]2Mn(SCN)4(4,4"-bipy).4H2O}n的合成和结构.《高等学校化学学报》.1998,第19卷(第10期),第1533-1536页. *

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