阅读说明：本技术 以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其制备方法和应用 (Dysprosium complex constructed by benzimidazole derivative and 1, 2-cyclohexanediamine as well as preparation method and application thereof ) 是由 邹华红 莫凯强 梁福沛 于 2019-09-05 设计创作，主要内容包括：本发明公开了一种以苯并咪唑衍生物和1,2-环己二胺构筑的镝配合物及其制备方法和应用。所述镝配合物的化学式为：[Dy(L1)(NO<Sub>3</Sub>)<Sub>2</Sub>(SCN)],L1表示N-甲基-苯并咪唑-2-醛；该镝配合物属于单斜晶系,P2<Sub>1</Sub>/n空间群。所述镝配合物的制备方法为：将N-甲基-苯并咪唑-2-醛、六水合硝酸镝、硫氰酸盐和1,2-环己二胺置于混合溶剂中,溶解后于加热或不加热条件下反应,反应物静置,有晶体析出,收集晶体,即得；其中,所述的混合溶剂为乙腈与甲醇或乙醇的组合物。本发明所述镝配合物为平面结构,对有机溶剂具有良好的发光响应,可用于检测或识别不同的有机溶剂,因此可用作敏化剂。(The invention discloses a dysprosium complex constructed by benzimidazole derivatives and 1, 2-cyclohexanediamine and a preparation method and application thereof. The chemical formula of the dysprosium complex is as follows: [ Dy (L1) (NO) 3 ) 2 (SCN)]L1 represents N-methyl-benzimidazole-2-aldehyde; the dysprosium complex belongs to a monoclinic system, P2 1 A/n space group. The preparation method of the dysprosium complex comprises the following steps: placing N-methyl-benzimidazole-2-aldehyde, dysprosium nitrate hexahydrate, thiocyanate and 1, 2-cyclohexanediamine in a mixed solvent, reacting under heating or non-heating conditions after dissolving, standing reactants, separating out crystals, and collecting the crystals to obtain the compound; wherein the mixed solvent is a composition of acetonitrile and methanol or ethanol. The dysprosium complex of the invention has a planar structure and is good for organic solventsGood luminescence response, can be used for detecting or identifying different organic solvents, and can be used as a sensitizer.)

1. The dysprosium complex constructed by benzimidazole derivatives and 1, 2-cyclohexanediamine is characterized in that:

the chemical formula of the dysprosium complex is as follows: [ Dy (L1) (NO)₃)₂(SCN)]Wherein L1 represents N-methyl-benzimidazole-2-aldehyde;

the dysprosium complex belongs to a monoclinic system, P2₁The/n space group, the unit cell parameters are: α＝90.00°，β＝90.684(9)°，γ＝90.00°。

2. dysprosium complexes constructed with benzimidazole derivatives and 1, 2-cyclohexanediamines as claimed in claim 1, wherein: placing N-methyl-benzimidazole-2-aldehyde, dysprosium nitrate hexahydrate, thiocyanate and 1, 2-cyclohexanediamine in a mixed solvent, reacting under heating or non-heating conditions after dissolving, standing reactants, separating out crystals, and collecting the crystals to obtain the compound; wherein the mixed solvent is a composition of acetonitrile and methanol or ethanol.

3. The method of claim 2, wherein: in the composition of the mixed solvent, the volume ratio of acetonitrile to methanol or ethanol is 1: 1-4.

4. The method of claim 2, wherein: the thiocyanate is sodium thiocyanate and/or potassium thiocyanate.

5. The method of claim 2, wherein: the reaction is carried out at a temperature of more than or equal to 50 ℃.

6. The method of claim 2, wherein: the reaction is carried out at 60-100 ℃.

7. Use of a dysprosium complex constructed from a benzimidazole derivative and 1, 2-cyclohexanediamine according to claim 1 for the preparation of a sensitizer.

Technical Field

The invention relates to a rare earth complex constructed by benzimidazole derivatives and 1, 2-cyclohexanediamine, in particular to a dysprosium complex constructed by benzimidazole derivatives and 1, 2-cyclohexanediamine and a preparation method and application thereof.

Background

Coordination chemistry plays a crucial role in the design of metal ion photoluminescent probes. Coordination of the metal with the organic dye causes a different optical reaction, which indicates the presence of the metal species of interest. d⁶、d⁸And d¹⁰The configured luminescent lanthanide and transition metal complexes tend to exhibit unique luminescent properties different from organic dyes, such as high quantum yield, large combustion volume, long emission wavelength and emission lifetime, low sensitivity to the microenvironment, and can be used as probes for metal ions, anions, and neutral species.

Due to the application of Volatile Organic Compounds (VOCs) in medicine, environmental science, toxicology, biochemistry, and the like, the analysis of volatile organic compounds has received much attention in recent years. They are useful for evaluating the properties and quality of industrial materials, detecting various diseases, and tracking air pollutants.

For over a decade, there has been an increasing interest in lanthanide complexes, especially because of their specific luminescent properties. Considering 4fⁿThe specific emission of the numerous electronic energy levels of the electronic configuration, ln (iii) ions, is mostly in the visible to infrared spectral range. The organic light-emitting ligand not only serves as a new construction body of a complex framework but also serves as Ln through the antenna effect³⁺High efficiency sensitizers for ions. Although lanthanide compounds have good luminescence property and regulation property, the luminescence response of the lanthanide compounds to volatile organic solvents is limited to lanthanide metal organic frameworks (Ln-MOFs) with three-dimensional network structures at present. The main response principle of Ln-MOFs is that organic matters enter pores of Ln-MOFs to cause effective MLCT generation, so that the luminous performance of the MLCT is changed. However, low-dimensional lanthanide compounds have little good luminescent response to specific organic substances, particularly zero-dimensional lanthanide coordination molecule clusters. Therefore, expanding the application of low-dimensional lanthanide compounds to the specific recognition of VOCs is a key and challenging task. However, no dysprosium complex which is constructed by benzimidazole derivatives and 1, 2-cyclohexanediamine and has a planar structure and a related report that the dysprosium complex has a good light-emitting response are found at present.

Disclosure of Invention

The invention aims to solve the technical problem of providing a planar azapolycyclic dysprosium complex which is constructed by benzimidazole derivatives and 1, 2-cyclohexanediamine and has good luminescent response to organic substances, and a preparation method and application thereof.

The dysprosium complex constructed by the benzimidazole derivative and the 1, 2-cyclohexanediamine has the chemical formula as follows: [ Dy (L1) (NO)₃)₂(SCN)]Wherein L1 represents N-methyl-benzimidazole-2-aldehyde; the dysprosium complex belongs to a monoclinic system, P2₁The/n space group, the unit cell parameters are: α＝90.00o，β＝90.684(9)^o，γ＝90.00o。

the invention also provides a preparation method of the dysprosium complex constructed by the benzimidazole derivative and the 1, 2-cyclohexanediamine in the claim 1, which comprises the following steps: placing N-methyl-benzimidazole-2-aldehyde, dysprosium nitrate hexahydrate, thiocyanate and 1, 2-cyclohexanediamine in a mixed solvent, reacting under heating or non-heating conditions after dissolving, standing reactants, separating out crystals, and collecting the crystals to obtain the compound; wherein the mixed solvent is a composition of acetonitrile and methanol or ethanol.

In the preparation method, the molar ratio of the N-methyl-benzimidazole-2-aldehyde to the dysprosium nitrate hexahydrate to the thiocyanate to the 1, 2-cyclohexanediamine is a stoichiometric ratio, and the amount of the dysprosium nitrate hexahydrate can be relatively excessive in the actual operation process. The thiocyanate is preferably sodium thiocyanate and/or potassium thiocyanate. In the composition of the mixed solvent, the volume ratio of acetonitrile to methanol or ethanol is 1: 1-4, more preferably 1: 1-2. The amount of the mixed solvent may be determined as required, and it is usually preferable that the raw materials for the reaction are dissolved. Specifically, the total amount of the mixed solvent used for all the raw materials is usually 6 to 15mL based on 1mmol of N-methyl-benzimidazole-2-aldehyde. In the specific dissolving step, the raw materials can be respectively dissolved by using a certain component in the mixed solvent and then mixed together for reaction; or mixing all the raw materials together and adding the mixed solvent for dissolving.

In the above production method, the reaction is preferably carried out under heating, more preferably at not less than 50 ℃ and still more preferably at 60 to 100 ℃. When the reaction is carried out at 60-100 ℃, the reaction time is usually controlled to 24-60 h.

In experiments, the applicant finds that the dysprosium complexes constructed by the benzimidazole derivatives and the 1, 2-cyclohexanediamine have different luminescence intensities in different organic solvents, and can be used for detecting or identifying different organic solvents. Therefore, the invention also comprises the application of the dysprosium complex constructed by the benzimidazole derivative and the 1, 2-cyclohexanediamine in preparing a sensitizer.

Compared with the prior art, the invention provides a planar aza-polycyclic dysprosium complex constructed by benzimidazole derivatives and 1, 2-cyclohexanediamine and a preparation method thereof, and the applicant finds in experiments that the dysprosium complex has good luminescent response to organic solvents, can be used for detecting or identifying different organic solvents, and can be used as a sensitizer.

Drawings

FIG. 1 is a crystal structure diagram of a final product obtained in example 1 of the present invention;

FIG. 2 is a thermogravimetric analysis plot of the final product made in example 1 of the present invention;

FIG. 3 is a powder diffraction pattern of the final product obtained in example 1 of the present invention;

FIG. 4 is a graph showing the UV-VIS absorption curve and the luminescence emission curve of a methanol solution of the final product obtained in example 1 of the present invention;

FIG. 5 is a diagram of the energy transfer process and the CIE color chart (i.e., color scale) of the final product of example 1 of the present invention, wherein (a) is the energy transfer process including the final product of example 1, and (b) is the CIE color chart including the final product of example 1;

FIG. 6 is a graph of the emission spectrum curves (313nm excitation) of the final products of example 1 of the present invention in different organic molecules (3mg/10 ml); wherein (a) is the emission spectrum curve (307nm excitation) of the final product obtained in example 1 in different organic molecules (3mg/10ml) and (b) is the bar graph of the luminescence intensity of the final product obtained in example 1 in different organic molecule solvents.

Detailed Description

The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.