CN108822303A - A kind of organic boron complexes and preparation method thereof with fluorescence property - Google Patents
A kind of organic boron complexes and preparation method thereof with fluorescence property Download PDFInfo
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- CN108822303A CN108822303A CN201811133027.2A CN201811133027A CN108822303A CN 108822303 A CN108822303 A CN 108822303A CN 201811133027 A CN201811133027 A CN 201811133027A CN 108822303 A CN108822303 A CN 108822303A
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Abstract
The invention discloses a kind of organic boron complexes and preparation method thereof with fluorescence property, the molecular formula of organic boron complexes are C27H21N4O3B, the crystal of the complex belong to monoclinic system, and cell parameter is：α=γ=90 °, β=97.730 (5) °；It include a boron atom, two benzimidazole ligands and a solvent methanol molecule in each asymmetric cell；In crystal, methanol molecules are not engaged in coordination as solvent, due to the presence of intermolecular hydrogen bonding, the structure of entire Crystallization one-dimensional chain.Invention also provides the preparation method of organic boron complexes, this method reaction condition is mild, and preparation process is simple, low in cost, has preferable thermal stability while the organic boron complexes of gained are with strong fluorescence.
Description
Technical field
The invention belongs to organic coordination compound synthesis technical fields, and in particular to a kind of organic boron cooperation with fluorescence property
Object and preparation method thereof.
Background technique
Important research theme one of of the organic coordination compound as current materials chemistry not only has aesthetics of structural design value, and
And it has a good application prospect in fields such as luminous, magnetism, absorption, hydrogen storage, catalysis and separation.Especially by metal ion
With organic multi-functional ligand coordination come constructed with high thermal stability structure and special type physical and chemical performance coordination polymer
Cause the great interest of people.However design and construct this kind of material with special construction and function and belong to innovative technology,
With very big challenge, the material of preferable thermal stability and fluorescence property is especially had both.In recent years, some to have high fever steady
It is qualitative, or the coordination polymer with fluorescence property has been widely studied, and achieves certain achievement, but in these coordinations
In polymer, while the material for having both preferable thermal stability and fluorescence property is but rarely reported.
Summary of the invention
To overcome problem above, the present invention provides a kind of organic boron complexes and preparation method thereof with fluorescence property,
This method reaction condition is mild, and preparation process is simple, low in cost, and the organic boron complexes of gained have preferable fluorescence simultaneously
Energy and thermal stability.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of organic boron complexes with fluorescence property, molecular formula C27H21N4O3The crystal of B, the complex belong to monoclinic crystal
System, cell parameter are： α=γ=90 °, β=
97.730(5)°；Include a boron atom, two benzimidazole ligands and a solvent methanol point in each asymmetric cell
Son；In crystal, boron atom take four-coordination form formed one distortion tetrahedral structure, methanol molecules as solvent simultaneously
Coordination is had neither part nor lot in, due to the presence of intermolecular hydrogen bonding, the structure of entire Crystallization one-dimensional chain.
Following technical scheme can be used also to realize in the object of the invention to solve the technical problems.
A kind of preparation method of organic boron complexes with fluorescence property, includes the following steps：
(1) 4mmol 2- (2- hydroxy benzenes) -1- hydrogen-benzimidazole and 2mmol triphenylborane are added to 20~25ml
In methanol solution, under agitation, heats the mixture to 80 DEG C and be stirred continuously holding at such a temperature 10~12 hours；
(2) the reacted solution of step (1) is subjected to vacuum drying treatment, crude product is obtained, then with petroleum ether/acetic acid second
Ester obtains sterling with silicagel column separating-purifying as eluant, eluent；Wherein, the volume ratio of petroleum ether and ethyl acetate is 1:3.
The preparation method of a kind of organic boron complexes with fluorescence property above-mentioned, wherein true described in step (2)
Sky, which is dried, to be carried out in Rotary Evaporators.
Compared with prior art, the present invention has the following advantages that：
(1) organic boron complexes of the invention have stronger fluorescence, complex during the preparation process, directly by ligand
It is reacted to obtain with triphenylborane, strong emission peak λ em=occurs under conditions of excitation spectrum is λ ex=350nm
385nm, its fluorescent emission may be mainly due to glimmering caused by the effect of the electron transmission (MLCT) between central atom-ligand
Light；
(2) the TG curve of organic boron complexes of the invention shows that the complex has preferable thermal stability, although
Solvent methanol molecule in 65 DEG C or so crystal starts to lose, but the basic framework of crystal still remains, and is continued until
400.3 DEG C of organic ligands just start weightlessness, and structural framing is caused to collapse；
(3) preparation process of the organic boron complexes of the present invention is simple, and high production efficiency, and equipment investment is few, while entire
Production process is substantially pollution-free, meets sustainable development requirement.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, special below to lift preferred embodiment, detailed description are as follows.
Detailed description of the invention
Fig. 1 is the organic boron complexes C of the present invention27H21N4O3The crystal structure of B.
Fig. 2 is the organic boron complexes C of the present invention27H21N4O3The three-dimensional space knot that B is formed due to pi-pi accumulation and hydrogen bond action
Structure.
Fig. 3 is the organic boron complexes C of the present invention27H21N4O3The TG curve of B.
Fig. 4 is the organic boron complexes C of the present invention27H21N4O3The fluorescence spectra of B, wherein Abs indicates absorption spectrum, PL table
Show fluorescence emission spectrum.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate,
Below in conjunction with attached drawing and preferred embodiment, a kind of organic boron with fluorescence property proposed according to the present invention is matched
Object and preparation method thereof is closed, specific embodiment, feature and its effect, detailed description is as follows.
Embodiment 1
Under the conditions of being stirred at room temperature, 0.841g (4mmol) 2- (2- hydroxy benzenes) -1- hydrogen-benzimidazole and 0.48g are weighed
(2mmol) triphenylborane is added in 20ml methanol solution, is heated to 80 DEG C and to be stirred continuously holding at such a temperature 12 small
When.Reacted solution is subjected to vacuum drying treatment in Rotary Evaporators, then with petrol ether/ethyl acetate (1:3) make
Sterling, yield 78% are obtained with silicagel column separating-purifying for eluant, eluent.
Embodiment 2
Under the conditions of being stirred at room temperature, 0.841g (4mmol) 2- (2- hydroxy benzenes) -1- hydrogen-benzimidazole and 0.48g are weighed
(2mmol) triphenylborane is added in 25ml methanol solution, is heated to 80 DEG C and to be stirred continuously holding at such a temperature 10 small
When.Reacted solution is subjected to vacuum drying treatment in Rotary Evaporators, then with petrol ether/ethyl acetate (1:3) make
Sterling, yield 76% are obtained with silicagel column separating-purifying for eluant, eluent.
Characterization detection is carried out to coordination polymer obtained by embodiment 1,2：
(1) crystal structure
The monocrystalline for choosing suitable size under the microscope is placed on Bruker SMART CCD AREA DETECTOR monocrystalline X-
On diffractometer, using graphite monochromatised Mo-Ka rayComplex exists at room temperature at 293 (2) K
On Bruker P4 four-circle diffractometer, at 293k with the Mo-K alpha ray through graphite monochromator monochromatization, at 4.14 °<θ<
Point diffraction 3541 are collected within the scope of 63.83 °, wherein independent point diffraction is 2233；All diffraction datas use SADABS
Program carries out absorption correction；Cell parameter is determined with least square method；Data convert and structure solution split not Shi Yong SAINT and
SHELXTL program is completed.Whole non-hydrogen atom coordinates first are determined with difference function method and least square method, and use theoretical hydrogenation method
Hydrogen atom position is obtained, refine then is carried out to crystal structure with least square method.The crystal structure and three-dimensional of the complex are tight
Close-packed structure schematic diagram is shown in Fig. 1, Fig. 2, and the partial parameters of crystallography point diffraction data collection and structure refinement see the table below 1：
The crystallography point diffraction data collection and structure refinement parameter of 1. embodiment 1 of table, 2 gained complexs
(2) differential thermal thermogravimetric analysis characterizes
Using the resistance to TG-DSC STA 449F1 type synchronous solving of speeding of Germany, with α-Al2O3For reference substance, in 200ml/
The stream of nitrogen gas of min is protected, and heating rate measures the TG curve of complex under conditions of being 5 DEG C/min.The coordination polymer
TG curve causes frame structure to be collapsed as shown in figure 3, organic ligand weightlessness since 400.3 DEG C, illustrates that gained complex has
Preferable thermal stability.
(3) Fluorescent Characterization
Fluorescence spectrum is measured using Edinburg BCEIA 2015FS5 type integration Fluorescence Spectrometer, at room temperature, is matched
Closing object, (concentration is 1.0 × 10 in methanol solution-6Mol/L it) measures, the fluorescence spectrum of the complex is as shown in figure 4, Fig. 4 shows
Gained complex is λ in excitation spectrumexOccurs strong emission peak λ under conditions of=350nmem=385nm illustrates the complex
With good fluorescent characteristic.Its fluorescent emission may be mainly due to the work of the electron transmission (MLCT) between central atom-ligand
The fluorescence caused by.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, this
The preferred embodiment of invention is not intended to limit the invention, any person skilled in the art, is not departing from skill of the present invention
In the range of art scheme, according to the technical essence of the invention it is to the above embodiments it is any it is simple modification, equivalent variations with
Modification, all of which are still within the scope of the technical scheme of the invention.
Claims (3)
1. a kind of organic boron complexes with fluorescence property, it is characterised in that its molecular formula is C27H21N4O3B, the complex
Crystal belongs to monoclinic system, and cell parameter is： α=
γ=90 °, β=97.730 (5) °；Include a boron atom, two benzimidazole ligands and one in each asymmetric cell
Solvent methanol molecule；In crystal, boron atom takes the form of four-coordination to form the tetrahedral structure distorted, methanol molecules
Coordination, the structure of entire Crystallization one-dimensional chain are had neither part nor lot in as solvent.
2. a kind of preparation method of organic boron complexes with fluorescence property, it is characterised in that include the following steps：
(1) 4mmol 2- (2- hydroxy benzenes) -1- hydrogen-benzimidazole and 2mmol triphenylborane are added to 20~25ml methanol
In solution, under agitation, heats the mixture to 80 DEG C and be stirred continuously holding at such a temperature 10~12 hours；
(2) the reacted solution of step (1) is subjected to vacuum drying treatment, obtains crude product, is then made with petrol ether/ethyl acetate
Sterling is obtained with silicagel column separating-purifying for eluant, eluent；Wherein, the volume ratio of petroleum ether and ethyl acetate is 1:3.
3. the preparation method of organic boron complexes with fluorescence property as claimed in claim 2, it is characterised in that step (2)
Described in vacuum drying treatment be to be carried out in Rotary Evaporators.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3621023A (en) * | 1968-05-27 | 1971-11-16 | American Cyanamid Co | 1,3,2-oxazaborinides and method for preparing the same |
| CN102993224A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex |
| CN103087113A (en) * | 2012-12-21 | 2013-05-08 | 南京邮电大学 | Boracic heteronuclear iridium complex and preparation method and application thereof |
| CN107445900A (en) * | 2017-08-09 | 2017-12-08 | 岭南师范学院 | A kind of benzimidazole part with chiral carbon, benzimidazole metal complex and its preparation method and application |
-
2018
- 2018-09-27 CN CN201811133027.2A patent/CN108822303B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3621023A (en) * | 1968-05-27 | 1971-11-16 | American Cyanamid Co | 1,3,2-oxazaborinides and method for preparing the same |
| CN102993224A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex |
| CN103087113A (en) * | 2012-12-21 | 2013-05-08 | 南京邮电大学 | Boracic heteronuclear iridium complex and preparation method and application thereof |
| CN107445900A (en) * | 2017-08-09 | 2017-12-08 | 岭南师范学院 | A kind of benzimidazole part with chiral carbon, benzimidazole metal complex and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| ZHENGYU ZHANG等: "2-(2-Hydroxyphenyl)benzimidazole-Based Four-Coordinate Boron-Containing Materials with Highly Efficient Deep-Blue Photoluminescence and Electroluminescence", 《INORGANIC CHEMISTRY》 * |
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