CN106867503B - Reversible force/heat/solvent multiple stimulation responsive materials and preparation method thereof that cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed - Google Patents
Reversible force/heat/solvent multiple stimulation responsive materials and preparation method thereof that cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Abstract
The invention discloses reversible force/heat/solvent multiple stimulation responsive materials and preparation method thereof that a kind of cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed.The off-color material is made to obtain two kinds of isomer α-[(Cu of solution evaporation method using cuprous iodide, three (4- chlorphenyl) phosphines as reaction raw materials4I4)L4] and β-[(Cu4I4)L4].250 °C of the material thermal decomposition temperature, performance is than allied substances (such as [Cu4I4L4] (L=tri- (4- anisyl) phosphine) more good stability.The material has the characteristics that preparation cost is low, operating method is simple, yield is high, stability is good, and material performance can be used as the novel pressure of one kind, temperature, solvent-susceptible material, for fields such as trademark anti-counterfeits to pressure, temperature, solvent-susceptible behavior.
Description
Technical field
The invention belongs to technical field of material, be related to a kind of cuprous iodide/tri- (4- chlorphenyl) phosphine construct it is reversible
Power/heat/solvent multiple stimulation responsive materials and preparation method thereof.
Background technique
It is that under external force, a kind of intellectual material of significant change occurs for luminescent color that power, which causes fluorescence off-color material,.Material
Material its absorption spectra after by external force changes, but is not related to the change of emission spectra.Change luminescent color by power
Approach there are two types of, first is that the change of chemical structure or chemical bond, second is that the variation for passing through state of aggregation.The former is to utilize grinding
The different fluorescence that the different molecular structure in front and back issues realize power mutagens color, the latter be then by change molecular stuffing mode,
The modes such as molecular conformation or intermolecular interaction change to realize.Temperature-sensitive material refers to that at different temperature material is sent out
Optical property or intensity change.Therefore this kind of stimuli responsive material is in pressure sensing, information storage, trademark anti-counterfeit and photophore
There is important potential application foreground on part.The invention mainly relates to pressure, thermal stimulus have response property can be mutual
Transition material.
Complex based on organic phosphorus/cuprous iodide cluster is due to the structural flexibility at cubane cuprous iodide center and abundant
d10-d10Interaction causes to play an important role in fluorescence off-color material in power.
Currently, the synthesis of such material has used the noble metals such as gold, iridium mostly, work to switch (on/off) mode
Intellectual material in its is at high cost；Secondly, many power, which cause off-color material, to be changed by regulation physics coherent condition,
Power is designed by the variation of regulation chemical bond causes the example of off-color material very few.This experiment is based on this and designs one
It is kind novel can phase co-conversion power mutagens color temperature sensitive material, not only method is simple for the technique, and preparation cost is low, has simultaneously
There is the structure sensitive material of pressure, temperature sensitivity feature, and the two can mutually change.This is in purposes such as detection, trademark anti-counterfeits
There is good prospect.
Summary of the invention
Based on above-mentioned analysis, the purpose of the present invention is to provide a kind of cuprous iodide/tri- (4- chlorphenyl) phosphine construct can
Inverse power/heat/solvent multiple stimulation responsive materials and preparation method thereof.It selects cheap cuprous iodide and three (4- chlorobenzenes
Base) phosphine is that reaction raw materials using simple solution evaporation method it is more to prepare a kind of novel cuprous iodide base reversible force/heat/solvent
Remise sharp responsive materials.Preparation method is simple, and raw material is inexpensive, and yield is high.It and is environment without noxious products in preparation process
Friendly green syt.
To achieve the above object, the present invention adopts the following technical scheme:
Two kinds can carry out reversible transformation structure sensitive material α-[(Cu4I4)L4] and β-[(Cu4I4)L4] structure difference
As shown in Figure 6 and Figure 7.
A kind of reversible force/heat/solvent multiple stimulation responsive materials that cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed, it is described
The molecular formula of cuprous iodide/tri- (4- chlorphenyl) phosphine is α-[(Cu4I4)L4] and β-[(Cu4I4)L4], L=tri- (4- chlorphenyl)
Phosphine, structure are four CuI3P tetrahedron is by total prismatic at the [(Cu of a cube of alkyl structure4I4)L4] cluster；α- [(Cu4I4)
L4] fluoresced green, space group is high symmetrical six sideR-3；β-[(Cu4I4)L4] hair yellow fluorescence, space group is monoclineC2/c。
At room temperature, α-[(Cu4I4)L4] green fluorescence is issued under the irradiation of ultraviolet light, it is ground to become yellow fluorescence, drop
Green fluorescence is restored to after adding acetonitrile.β-[(Cu4I4)L4] yellow fluorescence is sent out in the UV lamp, fluorescence color is kept not after grinding
Become, after acetonitrile is added dropwise, yellow fluorescence becomes green fluorescence.The XRD of two isomer grinding front and backs shows them by grinding
Mill realizes reversible transition, and is changed between yellow with shining by green.With the reduction of temperature, the fluorescence of two kinds of phases is strong
Degree gradually increases.The material also shows good stability, and 250 °C of thermal decomposition temperature, performance is than allied substances (such as [Cu4I4L4]
(L=tri- (4- anisyl) phosphine) more good stability.
Reversible force/the heat/solvent multiple stimulation responsive materials are the preparation method is as follows: by 0.01090g (0.1mmol)
Cuprous iodide is dissolved in 5 mL acetonitriles, and 0.0336g (0.1mmol) three (4- chlorphenyl) phosphine is dissolved in 10 mL ethanol solutions, and two
Person is mixed and stirred for, and filters after 10 min, and gained clear liquid stands volatilization at room temperature, obtains colourless transparent crystal afterwards for 24 hours, ultraviolet
Discovery jaundice color and green two kinds of different colours light after light irradiation, in the UV lamp according to luminescent color difference by two kinds of isomers
Manual separation carries out structure and performance test respectively.
Remarkable advantage of the invention is:
(1) present invention gained isomorphism Cu (I) complex being capable of reversible transition: at room temperature, the ultraviolet excitation through 365nm,
α-[(Cu4I4)L4] green fluorescence is issued, ground, fluorescence becomes yellow, after acetonitrile is added dropwise, is restored to green fluorescence.β-
[(Cu4I4)L4] hair yellow fluorescence, fluorescence color is constant after grinding, after acetonitrile is added dropwise, becomes green fluorescence.
(2) with the reduction of temperature, the fluorescence intensity of material is gradually increased.
(3) the raw materials used in the present invention is that commercially available cheap cuprous iodide, three (4- chlorphenyl) phosphines and acetonitrile and ethyl alcohol are molten
Agent；Its reaction can carry out at room temperature, and the reaction time is short, easy to operate；And obtained product purity is high, yield is big.
(4) material also shows good stability, and 250 °C of thermal decomposition temperature, performance is than allied substances (such as [Cu4I4L4]
(L=tri- (4- anisyl) phosphine) more good stability.
(5) material has the characteristics that preparation cost is low, operating method is simple, yield is high, stability is good, and material table
Now to pressure, temperature, solvent-susceptible behavior, the novel pressure of one kind, temperature, solvent-susceptible material can be used as, it is anti-for trade mark
The fields such as puppet.
Detailed description of the invention
Fig. 1 is reversible force/heat produced by the present invention/solvent multiple stimulation responsive materials infrared spectrogram；
Fig. 2 is reversible force/heat produced by the present invention/solvent multiple stimulation responsive materials UV-visible absorption spectrum；
Fig. 3 is reversible force/heat produced by the present invention/solvent multiple stimulation responsive materials XRD powder diagram；
Fig. 4 is reversible force/heat produced by the present invention/solvent multiple stimulation responsive materials fluorescence emission spectrum；
Fig. 5 is reversible force/heat produced by the present invention/solvent multiple stimulation responsive materials thermal multigraph；
Fig. 6 is α-[(Cu4I4)L4] structure chart；
Fig. 7 is β-[(Cu4I4)L4] structure chart.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further.
Embodiment 1
A kind of reversible force/heat/solvent multiple stimulation responsive materials that cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed, it is described
The molecular formula of cuprous iodide/tri- (4- chlorphenyl) phosphine is α-[(Cu4I4)L4] and β-[(Cu4I4)L4], L=tri- (4- chlorphenyl)
Phosphine, structure are four CuI3P tetrahedron is by total prismatic at the [(Cu of a cube of alkyl structure4I4)L4] cluster；α- [(Cu4I4)
L4] fluoresced green, space group is high symmetrical six sideR-3；β-[(Cu4I4)L4] hair yellow fluorescence, space group is monoclineC2/c。
At room temperature, α-[(Cu4I4)L4] green fluorescence is issued under the irradiation of ultraviolet light, it is ground to become yellow fluorescence, drop
Green fluorescence is restored to after adding acetonitrile；β-[(Cu4I4)L4] yellow fluorescence is sent out in the UV lamp, fluorescence color is kept not after grinding
Become, after acetonitrile is added dropwise, yellow fluorescence becomes green fluorescence；With the reduction of temperature, the fluorescence intensity of two kinds of phases is gradually increased.
Synthetic method includes the following steps: for 0.01090g (0.1mmol) cuprous iodide to be dissolved in 5 mL acetonitriles,
0.0336g (0.1mmol) three (4- chlorphenyl) phosphine is dissolved in 10 mL ethanol solutions, and the two is mixed and stirred for, mistake after 10 min
Filter, gained clear liquid stands volatilization at room temperature, obtains colourless transparent crystal afterwards for 24 hours, and discovery is turned to be yellow color and green after ultraviolet light irradiation
Two kinds of isomers manual separations are carried out structure according to luminescent color difference in the UV lamp by two kinds of different colours light of color respectively
And performance test.
Product characterization
1. Crystal Structure:
Structural characterization is carried out to single crystal samples using X-ray single crystal diffractometer.Details are as follows: instrument Brucker
Company's monocrystalline Apex Duo CCD x-ray diffractometer.X-ray source is Mo target, wavelength 0.71073, graphite monochromator.Withω
Scanning mode collects point diffraction, data acquired warpLpCorrection is chosenI>2σ(I) independent point diffraction for mono-crystalline structures point
Analysis.The initial configuration of crystal and refine useSHELX- 97 structure elucidation programs are completed, initial configuration mode direct method solution
Out, the coordinate of non-hydrogen atom and anisotropic temperature factor use complete matrix least square method to carry out structure refinement, hydrogen atom
Coordinate is found out and is fixed from geometric position, and isotropic temperature factor participates in Structure Calculation, but is not involved in the essence of structure
It repairs.The mathematical expressions such as least square function used in structural analysis process, discrepancy factor, weight discrepancy factor, weight factor
Formula is as follows:
Least square function:
Temperature factor:
Discrepancy factor:
Weight discrepancy factor:
Weight factor:,
Crystal structure analysis shows sample α-[(Cu4I4)L4] it is hexagonal crystal system, space group isR-3。β-[(Cu4I4)L4] be
Monoclinic system, space group areC2/c.Classical Cu is presented in they4I4Cube alkane structure, this cube of alkyl structure are four CuI3P
Tetrahedron by total prismatic at.Its actual crystal data, atomic coordinates and effective homogeneity displacement parameter, selection bond distance and
Bond angle is shown in Table 1,2,3 respectively.
The crystallographic data of 1 Sample crystals structure of table
2 α of table-[(Cu4I4)L4] atomic coordinates (× 104) and effective homogeneity displacement parameter (2×103)
3 β of table-[(Cu4I4)L4] atomic coordinates (× 104) and effective homogeneity displacement parameter (2×103)
4 α of table-[(Cu4I4)L4] selection bond distance () and bond angle (°)
Symmetry transformations used to generate equivalent atoms: #1 -y+1,
x-y,z； #2 -x+y+1,-x+1,z
5 β of table-[(Cu4I4)L4] selection bond distance () and bond angle (°)
Symmetry transformations used to generate equivalent atoms: #1 -x,y,-
z+1/2
2. infrared spectrum characterization:
Infrared spectroscopy survey is carried out with ATR method to sample using 2000 infrared spectrometer of Perkin-Elmer Spectrum
Examination, gained infrared spectrogram are shown in Fig. 1, and each absorption peak of spectrogram and ownership are as shown in table 6.
6 ultra-red vibration frequency of table and ownership
| Ownership | Peak position (cm-1) |
| ν Ar-H | 3048 |
| Phenyl ring stretching vibration | 1570,1389 |
| ν CH-P | 1479 |
| δC-H | 1084,1009 |
| ν C-Cl | 808 |
| δ=CH | 738,698 |
Ultraviolet-ray visible absorbing:
The uv-visible absorption spectra test of sample uses 800 type UV/Vis spectrometer of Perkin-Elmer Lambda
It measures at room temperature, uv-visible absorption spectra is shown in Fig. 2.
From figure 2 it can be seen that sample has a absorption peak at 340nm, this absorption peak comes from ligand three (4- chlorphenyl)
Phosphine ligands, π-π * transition of the corresponding electron transition in respective ligand.
4. XRD powder diagram:
Sample is tested using the XRD powder diffractometer from Rigaku Ultima, XRD powder diagram is shown in
Fig. 3.
As can be seen from the figure α-[(Cu4I4)L4] simulation drawing with before the milling, after recrystallization and β-[(Cu4I4)L4]
Spectrogram after re-crystallization is consistent substantially.Similarly, β-[(Cu is also given in figure4I4)L4Grinding front and back and β-
[(Cu4I4)L4] powder diagram after grinding is consistent substantially with the spectrogram come is simulated.Showing to realize can anti-phase
Become.
5. luminescent properties are tested:
Utilize the luminous light of Edinburgh Instrument F900 spectrometer test sample crystal phase at different temperatures
Spectrum.
Emission spectra under Fig. 4 different temperatures.Under the excitation wavelength of 365nm, α-[(Cu4I4)L4] emission peak is
520nm, β-[(Cu4I4)L4For 550nm.And shining for the compound has apparent temperature sensitivity matter: from 297K-77K,
With the reduction of temperature, luminous intensity is gradually increased.When sample temperature restores to room temperature, fluorescence intensity, which is also restored back to, to be come, can
See that it responds phenomenon with reversible thermal stimulus.
6, performance for stability is tested:
Chlorine atom in L=tri- (4- chlorphenyl) phosphine can form intramolecular and intermolecular hydrogen bonding as electron acceptor, thus make
The stability for obtaining material greatly improves.And in L=tri- (4- anisyl) phosphine, C-O ehter bond is weaker, and material is sent out at a lower temperature
Solution estranged.Therefore in this patent, the introducing of electron-withdrawing group is conducive to improve stability of material on phenyl ring.
Claims (3)
1. a kind of reversible force/heat/solvent multiple stimulation responsive materials that cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed, feature
It is, the molecular formula of cuprous iodide/tri- (4- chlorphenyl) phosphine is α-[(Cu4I4)L4] or β-[(Cu4I4)L4], L=tri-
(4- chlorphenyl) phosphine, structure are four CuI3P tetrahedron is by total prismatic at the [(Cu of a cube of alkyl structure4I4)L4] cluster；
α- [(Cu4I4)L4] fluoresced green, space group is high symmetrical six sideR- 3, cell parameter:a=16.6422 (10),
α=90 °,b=16.6422 (10), β=90 °,c=52.722 (6), γ=120 °, unit-cell volume: 12646 (2), no
Symmetrical cell number: 6；β-[(Cu4I4)L4] hair yellow fluorescence, space group is monoclineC2/c, cell parameter:a = 21.075(3)
, α=90 °,b=14.7856 (17), β=90.993 (2) °,c=25.496 (3), γ=90 °, unit-cell volume:
7943.5 (17), asymmetric cell number: 4；α-[(Cu4I4)L4] and β-[(Cu4I4)L4] structural formula it is as follows:
。
2. reversible force/heat/solvent that a kind of cuprous iodide/tri- (4- chlorphenyl) phosphine according to claim 1 is constructed is multiple
Stimuli responsive material, which is characterized in that at room temperature, α-[(Cu4I4)L4] green fluorescence is issued under the irradiation of ultraviolet light, through grinding
Mill becomes yellow fluorescence, is restored to green fluorescence after acetonitrile is added dropwise；β-[(Cu4I4)L4] yellow fluorescence is sent out in the UV lamp, it grinds
Fluorescence color remains unchanged afterwards, and after acetonitrile is added dropwise, yellow fluorescence becomes green fluorescence；With the reduction of temperature, two kinds of phases
Fluorescence intensity gradually increases.
3. a kind of reversible force/heat/solvent for preparing cuprous iodide/tri- as claimed in claim 1 or 2 (4- chlorphenyl) phosphine and constructing
The method of multiple stimulation responsive materials, which is characterized in that synthetic method includes the following steps: 0.1mmol cuprous iodide being dissolved in 5
In mL acetonitrile, 0.1mmol tri- (4- chlorphenyl) phosphine is dissolved in 10 mL ethanol solutions, and the two is mixed and stirred for, mistake after 10 min
Filter, gained clear liquid stand volatilization at room temperature, obtain colourless transparent crystal afterwards for 24 hours, discovery crystal jaundice color after ultraviolet light irradiation
With green two kinds of different colours light, in the UV lamp according to luminescent color difference by two kinds of isomers manual separations, described in acquisition
Reversible force/heat/solvent multiple stimulation responsive materials.
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| CN107602593B (en) * | 2017-10-31 | 2019-06-18 | 江西理工大学 | A kind of application of four core copper [I] complex of o-methyl pyridine tetrazole in stimuli responsive color-changing materials |
| CN108102639B (en) * | 2017-12-27 | 2020-07-31 | 内蒙古大学 | Preparation method of anti-counterfeiting material with multiple optical signal responses regulated and controlled by spin conversion |
| CN109580529A (en) * | 2019-01-25 | 2019-04-05 | 哈尔滨商业大学 | Malachite green-boric acid system thermochromic material and ratio confirmation test method |
| CN109651408B (en) * | 2019-01-26 | 2021-04-13 | 济宁学院 | Novel CuI complex and preparation method and application thereof |
| CN110511743B (en) * | 2019-09-09 | 2020-09-29 | 苏州大学 | Fluorescent photochromic material and preparation method and application thereof |
| CN113025316B (en) * | 2021-03-15 | 2021-12-28 | 山东大学 | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED |
| CN113025107B (en) * | 2021-05-10 | 2021-12-21 | 中山大学 | Preparation method and application of cuprous iodide-based hybrid fluorescent coating |
| CN115872975B (en) * | 2023-01-06 | 2023-05-12 | 暨南大学 | Annular trinuclear cuprous complex and preparation method and application thereof |
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