CN108949160A - A kind of fluorenes class organic compound and preparation method thereof with fluorescence property - Google Patents
A kind of fluorenes class organic compound and preparation method thereof with fluorescence property Download PDFInfo
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- CN108949160A CN108949160A CN201811133028.7A CN201811133028A CN108949160A CN 108949160 A CN108949160 A CN 108949160A CN 201811133028 A CN201811133028 A CN 201811133028A CN 108949160 A CN108949160 A CN 108949160A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The fluorenes class organic compound and preparation method thereof with fluorescence property that the invention discloses a kind of, the structural unit of gained fluorenes class organic compound belong to monoclinic system, molecular formula C35H22IN3, molecular weight 611.46, space group P21/n, cell parameter are as follows:α=γ=90 °, β=100.214 (2) °；A carbon atom in the fluorenes class organic compound takes sp3Center of the hydridization as entire molecule links together two rigid fluorenes rings, and two rigid fluorenes ring planes almost vertically exist, and angle is 89.37 ° (0.05), and the average deviation of two rigid fluorenes ring planes isWithInvention also provides the preparation methods of the fluorenes class organic compound, and this method reaction condition is mild, and preparation process is simple, low in cost, have preferable stability while gained compound is with strong fluorescence performance.
Description
Technical field
The invention belongs to the synthesis technical fields of luminous organic material, and in particular to a kind of fluorenes class with fluorescence property has
Machine compound and preparation method thereof.
Background technique
Organic conjugate material is drawn as the potential using value possessed by the fields such as electronics, luminous and nonlinear optics
Play people's extensive concern.Mostly with conjugation heterocycle and various chromophores in the structure of this kind of material, such as: carbazole, dislikes two at thiazole
Azoles, cumarin, fluorenes and 1,3-butadiene derivative etc., compared with other organic conjugate materials, fluorenes and its derivative have very
Mostly significant advantage: fluorenes ring is the coplanar biphenyl structural of rigidity, the methylene in structural formula between two phenyl ring due to by
The influence of phenyl ring, 9 hydrogen is quite active, can be easily introduced various substituent groups to improve its solubility property and supermolecule
Structure, and the influence that apparent steric hindrance will not be caused to be conjugated main chain, thus, fluorenes ring has good repair in structure
Decorations property.In non-linear optical field, fluorenes ring is as a kind of outstanding non-linear chromophore, by changing electron donor or receptor
The length of electronic capability and conjugated chain is pushed and pulled, it is some organic with big two photon absorption cross section and strong two-photon fluorescence
Two-photon material has been reported, but in these molecular materials, while having both the material of preferable thermal stability and fluorescence property but
It is rarely reported.
Summary of the invention
To overcome problem above, the present invention provides a kind of fluorenes class organic compound with fluorescence property and its preparation side
Method, this method reaction condition is mild, and preparation process is simple, low in cost, and gained fluorenes class organic compound has preferably simultaneously
Fluorescence property 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 fluorenes class organic compound with fluorescence property, the structural unit of the fluorenes class organic compound is monoclinic system, molecule
Formula is C35H22IN3, molecular weight 611.46, space group P21/n, cell parameter are as follows:α=γ=90 °, β=100.214
(2)°；A carbon atom in the fluorenes class organic compound takes sp3Center of the hydridization as entire molecule, by two rigid fluorenes
Ring links together, and two fluorenes ring planes almost vertically exist, and angle is 89.37 ° (0.05), and two rigid fluorenes ring planes
Average deviation beWith
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 the fluorenes class organic compound with fluorescence property, comprising the following steps:
It (1) is that 1:1 is dissolved in glacial acetic acid and sulfuric acid according to the ratio between amount of substance by 4,5- carboline -9- ketone and elemental iodine
In the mixed solvent is heated to 80 DEG C and flows back 6 hours at such a temperature, filters after being cooled to room temperature, obtain white solid, will
Gained white solid is soluble in water, is extracted with chloroform, is then dried in vacuo, and it is stand-by to obtain intermediate products 1；
(2) under nitrogen protection, hub products 1, magnesium powder and 2- bromo biphenyl are added to according to the ratio between amount of substance for 1:1:1
It in tetrahydrofuran solution after slow reaction 12 hours, is extracted with chloroform, rotates drying, the solid after drying is then dissolved in acetic acid
In, it is heated to 80 DEG C and flows back 24 hours at such a temperature, be cooled to room temperature, adjusted with sodium hydroxide solution after flowing back and cooling down
The pH value of material be neutrality, extracted with chloroform, it is stand-by to obtain intermediate products 2；
It (3) is that 2:3:6:2 is added to neighbour according to the ratio between amount of substance by intermediate products 2 and diphenylamines, potassium carbonate, copper oxide
In dichlorobenzene solution, it is heated to 80 DEG C and flows back 18 hours at such a temperature, then using petrol ether/ethyl acetate as elution
Agent obtains sterling with silicagel column separating-purifying；Wherein, the volume ratio of petroleum ether and ethyl acetate is 1:3.
The preparation method of a kind of fluorenes class organic compound with fluorescence property above-mentioned, wherein described in step (1)
The volume ratio of in the mixed solvent glacial acetic acid and sulfuric acid is 4:1.
Compared with prior art, the invention has the following advantages that
(1) gained fluorenes class organic compound has preferable fluorescence property, is λ in excitation spectrumexUnder conditions of=392nm
There is strong emission peak λem=480nm, its fluorescent emission may be mainly due to electron donating group and jump in the absorption of long-wavelength region
It moves；
(2) the TG curve of gained fluorenes class organic compound shows that the compound has preferable thermal stability, holds always
Continue 360 DEG C or so compounds and just start weightlessness, structural framing is caused to collapse.Stabilization of the higher decomposition temperature to luminescent material
Property has great importance；
(3) the method for the present invention reaction condition is mild, and preparation process is simple, low in cost, and gained fluorenes class organic compound is not
Only there is stronger fluorescence, while there is preferable thermal stability.
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 organic compound C35H22IN3Crystal structure.
Fig. 2 is organic compound C35H22IN3TG curve.
Fig. 3 is organic compound C35H22IN3Fluorescence spectra.
Fig. 4 is organic compound C35H22IN3Synthetic route chart.
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
Preferred embodiment, to a kind of fluorenes class organic compound and preparation method thereof with fluorescence property proposed according to the present invention,
Specific embodiment, feature and its effect, detailed description is as follows.
Embodiment 1
(1) it weighs 4.5g (25mmol) 4,5- carboline -9- ketone and 6.35g (25mmol) elemental iodine is dissolved in 40ml ice vinegar
The in the mixed solvent of acid and 10ml sulfuric acid is heated to 80 DEG C and flows back 6 hours at such a temperature, filters after being cooled to room temperature,
Obtain white solid, gained white solid is soluble in water, extracted with chloroform, be then dried in vacuo, obtain intermediate products 1 to
With yield 85%；
(2) under nitrogen protection, 4.3g (10mmol) hub products 1,0.24g (10mmol) magnesium powder and 2.3g are weighed
(10mmol) 2- bromo biphenyl is dissolved in 30ml tetrahydrofuran solution after slow reaction 12 hours, is extracted with chloroform, and revolving is dry
It is dry, then the solid after drying is dissolved in 40ml acetic acid, 80 DEG C is heated to and flows back 24 hours at such a temperature, be cooled to room
Temperature, adjusts reflux with sodium hydroxide and material pH value after cooling is neutrality, is extracted with chloroform, obtains intermediate products 2 for use, produces
Rate 70%；
(3) weigh 1.1g (2mmol) intermediate products 2,0.51g, (3mmol) diphenylamines, 0.83g (6mmol) potassium carbonate,
0.16g (2mmol) copper oxide is added in 40ml o-dichlorobenzene solution according to the ratio between the amount of substance 2:3:6:2, is heated to 80 DEG C
And flow back 18 hours at such a temperature, then using petrol ether/ethyl acetate (1:3) as eluant, eluent, with silicagel column separating-purifying,
Obtain sterling, yield 63%.
Characterization detection is carried out to coordination polymer obtained by embodiment 1:
(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, 3.58 ° < θ <
Point diffraction 5763 are collected within the scope of 26.37 °, wherein independent point diffraction is 4672；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 of the coordination polymer is illustrated
Figure is shown in Fig. 1, 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. gained coordination polymer of table
(2) differential thermal thermogravimetric analysis characterizes
Using the resistance to 449 F1 type synchronous solving of TG-DSC STA of speeding of Germany, with α-Al2O3For reference substance, in 200ml/
The N of min2Air-flow protection, heating rate measure the TG-DSC curve of coordination polymer under conditions of being 5 DEG C/min.The polycomplexation
The TG curve of object is closed as shown in Fig. 2, organic ligand weightlessness since 360 DEG C, causes frame structure to be collapsed, the surface coordination polymerization
Object has preferable thermal stability, and higher decomposition temperature has great importance to the stability of luminescent material.
(3) Fluorescent Characterization
Fluorescence spectrum is measured using 2015 FS5 type integration Fluorescence Spectrometer of Edinburg BCEIA, at room temperature,
(concentration is 1.0 × 10 to coordination polymer in DMF solution-6Mol/L it) measures.The fluorescence spectrum of the coordination polymer such as Fig. 3 institute
Show.Coordination polymer obtained by showing is λ in excitation spectrumexOccurs strong emission peak λ under conditions of=392nmem=480nm, says
The fluorescent characteristic that the bright coordination polymer has had.Its fluorescent emission may be mainly due to electron donating group in long-wavelength region
Absorptive transition.
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 fluorenes class organic compound with fluorescence property, it is characterised in that the structural unit of the fluorenes class organic compound is
Monoclinic system, molecular formula C35H22IN3, molecular weight 611.46, space group P21/n, cell parameter are as follows:α=γ=90 °, β=100.214 (2) °；
A carbon atom in the fluorenes class organic compound takes sp3Center of the hydridization as entire molecule connects two rigid fluorenes rings
It is connected together, the angle of two fluorenes ring planes is 89.37 ° (0.05), and the average deviation of two rigid fluorenes ring planes isWith
2. a kind of preparation method of the fluorenes class organic compound with fluorescence property, it is characterised in that the following steps are included:
(1) by 4,5- carboline -9- ketone and elemental iodine according to the mixing that the ratio between amount of substance is that 1:1 is dissolved in glacial acetic acid and sulfuric acid
In solvent, it is heated to 80 DEG C and flows back 6 hours at such a temperature, filtered after being cooled to room temperature, obtain white solid, by gained
White solid is soluble in water, is extracted with chloroform, is then dried in vacuo, and it is stand-by to obtain intermediate products 1；
(2) under nitrogen protection, hub products 1, magnesium powder and 2- bromo biphenyl are added to tetrahydro according to the ratio between amount of substance for 1:1:1
It in tetrahydrofuran solution after slow reaction 12 hours, is extracted with chloroform, rotates drying, then the solid after drying is dissolved in acetic acid,
It is heated to 80 DEG C and flows back 24 hours at such a temperature, be cooled to room temperature, flowed back with sodium hydroxide solution adjusting and after cooling
The pH value of material is neutrality, is extracted with chloroform, and it is stand-by to obtain intermediate products 2；
It (3) is that 2:3:6:2 is added to adjacent dichloro according to the ratio between amount of substance by intermediate products 2 and diphenylamines, potassium carbonate, copper oxide
In benzole soln, it is heated to 80 DEG C and flows back 18 hours at such a temperature, then using petrol ether/ethyl acetate as eluant, eluent, use
Silicagel column separating-purifying, obtains sterling；Wherein, the volume ratio of petroleum ether and ethyl acetate is 1:3.
3. the preparation method of the fluorenes class organic compound with fluorescence property as claimed in claim 2, it is characterised in that step
(1) volume ratio of in the mixed solvent glacial acetic acid and sulfuric acid described in is 4:1.
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Cited By (1)
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| CN111892628A (en) * | 2020-08-21 | 2020-11-06 | 郑州大学 | Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof |
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| CN102617466A (en) * | 2011-12-31 | 2012-08-01 | 上海师范大学 | Top-bottom asymmetrical tert-butyl spirobifluorene compound |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111892628A (en) * | 2020-08-21 | 2020-11-06 | 郑州大学 | Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof |
| CN111892628B (en) * | 2020-08-21 | 2021-05-11 | 郑州大学 | Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof |
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