CN106867503A - Reversible force/heat/solvent multiple stimulation responsive materials that cuprous iodide/tri- (4 chlorphenyl) phosphine is constructed and preparation method thereof - Google Patents
Reversible force/heat/solvent multiple stimulation responsive materials that cuprous iodide/tri- (4 chlorphenyl) phosphine is constructed and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 230000002441 reversible effect Effects 0.000 title claims abstract description 21
- 229910021595 Copper(I) iodide Inorganic materials 0.000 title claims abstract description 19
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 title claims abstract description 18
- 230000000638 stimulation Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 206010023126 Jaundice Diseases 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 150000004694 iodide salts Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- DCYICVONOLZQJK-UHFFFAOYSA-N (4-chlorophenyl)phosphane Chemical class PC1=CC=C(Cl)C=C1 DCYICVONOLZQJK-UHFFFAOYSA-N 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 230000008859 change Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000003471 mutagenic agent Substances 0.000 description 2
- 231100000707 mutagenic chemical Toxicity 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical class ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012926 crystallographic analysis Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- TXWRERCHRDBNLG-UHFFFAOYSA-N cubane Chemical compound C12C3C4C1C1C4C3C12 TXWRERCHRDBNLG-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- 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
- 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
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Abstract
Reversible force/heat/solvent multiple stimulation responsive materials constructed the invention discloses a kind of cuprous iodide/tri- (4 chlorphenyl) phosphine and preparation method thereof.The off-color material is made of solution evaporation method and obtains two kinds of isomer α [(Cu with cuprous iodide, three (4 chlorphenyl) phosphines as reaction raw materials4I4)L4] and β [(Cu4I4)L4].Allied substances are compared in 250 °C of the material thermal decomposition temperature, performance（Such as [Cu4I4L4] (L=tri- (4 anisyl) phosphine) better stability.The material has that preparation cost is low, operating method is simple, yield is high, good stability the features such as, and material performance is to pressure, temperature, solvent-susceptible behavior, can be as a kind of new pressure, temperature, solvent-susceptible material, for fields such as trademark anti-counterfeits.
Description
Technical field
The invention belongs to technical field of material, be related to that a kind of cuprous iodide/tri- (4- chlorphenyls) phosphine constructs is reversible
Power/heat/solvent multiple stimulation responsive materials and preparation method thereof.
Background technology
It is that under external force, glow color occurs a class intellectual material of significant change that power causes fluorescence off-color material.Material
Material its absorption spectra after being acted on by external force changes, but is not related to the change of emission spectra.Glow color is changed by power
Approach have two kinds, one is the change of chemical constitution or chemical bond, and two is by the change of state of aggregation.The former is using grinding
The different fluorescence that front and rear different molecular structure sends realize power mutagens color, the latter be then by change molecular stuffing mode,
The mode such as molecular conformation or intermolecular interaction come realize change.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 Store, trademark anti-counterfeit and photophore
There is important potential application foreground on part.Can be mutual the invention mainly relates to what there is response property to pressure, thermal stimulus
Transition material.
Complex based on organophosphor/cuprous iodide cluster is due to the structural flexibility at cubane cuprous iodide center and abundant
d10-d10Interact and cause to occupy critical role in fluorescence off-color material in power.
At present, the synthesis of such material has been used mostly the noble metals such as gold, iridium, is being used to switch（on/off）Mode works
Intellectual material in its high cost；Secondly, many power cause off-color material is changed by regulating and controlling physics coherent condition,
The example of off-color material is caused to can be counted on one's fingers to design power by regulating and controlling the change of chemical bond.This experiment is based on this and designs one
It is kind new can phase co-conversion power mutagens color temperature sensitive material, not only method is simple for the technique, and preparation cost is low, while tool
There are pressure, the structure sensitive material of temperature sensitivity feature, and the two can mutually change.This is in purposes such as detection, trademark anti-counterfeits
There is good prospect.
The content of the invention
Based on above-mentioned analysis, it is an object of the invention to provide a kind of cuprous iodide/tri- (4- chlorphenyls) 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 be reaction raw materials, using simple solution evaporation method, prepare a kind of new cuprous iodide base reversible force/heat/solvent many
Remise sharp responsive materials.Its preparation method is simple, and raw material is inexpensive, and yield is high.And it is environment without noxious products in preparation process
Friendly green syt.
To achieve the above object, the present invention is adopted the following technical scheme that：
Two kinds can carry out reversible transformation structure sensitive material α-[(Cu4I4)L4] and β-[(Cu4I4)L4] structure respectively such as Fig. 6
With shown in Fig. 7.
Reversible force/heat that a kind of cuprous iodide/tri- (4- chlorphenyls) phosphine is constructed/solvent multiple stimulation responsive materials, the iodate
The molecular formula of cuprous/tri- (4- chlorphenyls) phosphines is α-[(Cu4I4)L4] and β-[(Cu4I4)L4], L=tri- (4- chlorphenyls) phosphine,
Its structure is four CuI3P tetrahedrons are by common prismatic into a cube of [(Cu for alkyl structure4I4)L4] cluster；α- [(Cu4I4)L4]
Fluoresced green, its space group is six symmetrical sides highR-3；β-[(Cu4I4)L4] hair yellow fluorescence, space group is monoclineC 2/
c。
At room temperature, α-[(Cu4I4)L4] green fluorescence is sent under the irradiation of ultraviolet light, it is ground to be changed into yellow fluorescence, drop
Plus green fluorescence is returned to after acetonitrile.β-[(Cu4I4)L4] yellow fluorescence is issued in uviol lamp, fluorescence color keeps not after grinding
Become, after acetonitrile is added dropwise, yellow fluorescence is changed into green fluorescence.XRD before and after two isomer grindings shows that they are by grinding
Mill realizes reversible transition, and is changed between yellow by green with luminous.With the reduction of temperature, the fluorescence of two kinds of phases is strong
Degree gradually strengthens.The material also shows good stability, and allied substances are compared in 250 °C of heat decomposition temperature, performance（Such as [Cu4I4L4]
(L=tri- (4- anisyls) phosphine) better stability.
The preparation method of the reversible force/heat/solvent multiple stimulation responsive materials is as follows：By 0.01090g (0.1mmol)
Cuprous iodide is dissolved in 5 mL acetonitriles, and 0.0336g (0.1mmol) three (4- chlorphenyls) phosphine is dissolved in 10 mL ethanol solutions, two
Person is mixed and stirred for, and is filtered after 10 min, and gained clear liquid stands volatilization, colourless transparent crystal is obtained after 24h at room temperature, ultraviolet
Jaundice color and green two kinds of different colours light are found after light irradiation, it is different by two kinds of isomers according to glow color under uviol lamp
Manual separation, carries out structure and performance test respectively.
Remarkable advantage of the invention is：
（1）Gained isomorphism Cu (I) complex of the invention being capable of reversible transition：At room temperature, through the ultraviolet excitation of 365nm, α-
[(Cu4I4)L4] green fluorescence is sent, ground, fluorescence is changed into yellow, after acetonitrile is added dropwise, returns to green fluorescence.β-
[(Cu4I4)L4] hair yellow fluorescence, fluorescence color is constant after grinding, after acetonitrile is added dropwise, is changed into green fluorescence.
（2）With the reduction of temperature, the fluorescence intensity of material gradually strengthens.
（3）It is that commercially available cheap cuprous iodide, three (4- chlorphenyls) phosphines and acetonitrile and ethanol are molten that the present invention is raw materials used
Agent；Its reaction can be carried out at room temperature, and the reaction time is short, simple to operate；And the product purity that obtains is high, yield is big.
（4）The material also shows good stability, and allied substances are compared in 250 °C of heat decomposition temperature, performance（Such as [Cu4I4L4]
(L=tri- (4- anisyls) phosphine) better stability.
（5）The material has that preparation cost is low, operating method is simple, yield is high, good stability the features such as, and material list
Now to pressure, temperature, solvent-susceptible behavior, can be anti-for trade mark as a kind of new pressure, temperature, solvent-susceptible material
The fields such as puppet.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of reversible force/heat obtained in the present invention/solvent multiple stimulation responsive materials；
Fig. 2 is the UV-visible absorption spectrum of reversible force/heat obtained in the present invention/solvent multiple stimulation responsive materials；
Fig. 3 is the XRD powder diagrams of reversible force/heat obtained in the present invention/solvent multiple stimulation responsive materials；
Fig. 4 is the fluorescence emission spectrum of reversible force/heat obtained in the present invention/solvent multiple stimulation responsive materials；
Fig. 5 is the thermal multigraph of reversible force/heat obtained in the present invention/solvent multiple stimulation responsive materials；
Fig. 6 is α-[(Cu4I4)L4] structure chart；
Fig. 7 is β-[(Cu4I4)L4] structure chart.
Specific embodiment
In order that content of the present invention easily facilitates understanding, with reference to specific embodiment to of the present invention
Technical scheme is described further.
Embodiment 1
Reversible force/heat that a kind of cuprous iodide/tri- (4- chlorphenyls) phosphine is constructed/solvent multiple stimulation responsive materials, the iodate
The molecular formula of cuprous/tri- (4- chlorphenyls) phosphines is α-[(Cu4I4)L4] and β-[(Cu4I4)L4], L=tri- (4- chlorphenyls) phosphine,
Its structure is four CuI3P tetrahedrons are by common prismatic into a cube of [(Cu for alkyl structure4I4)L4] cluster；α- [(Cu4I4)L4]
Fluoresced green, its space group is six symmetrical sides highR-3；β-[(Cu4I4)L4] hair yellow fluorescence, space group is monoclineC 2/
c。
At room temperature, α-[(Cu4I4)L4] green fluorescence is sent under the irradiation of ultraviolet light, it is ground to be changed into yellow fluorescence, drop
Plus green fluorescence is returned to after acetonitrile；β-[(Cu4I4)L4] yellow fluorescence is issued in uviol lamp, fluorescence color keeps not after grinding
Become, after acetonitrile is added dropwise, yellow fluorescence is changed into green fluorescence；With the reduction of temperature, the fluorescence intensity of two kinds of phases gradually strengthens.
Synthetic method comprises the following steps：0.01090g (0.1mmol) cuprous iodide is dissolved in 5 mL acetonitriles,
0.0336g (0.1mmol) three (4- chlorphenyls) phosphine is dissolved in 10 mL ethanol solutions, and both are mixed and stirred for, mistake after 10 min
Filter, gained clear liquid stands volatilization, colourless transparent crystal obtained after 24h at room temperature, and find to turn to be yellow color and green after ultra violet lamp
Two kinds of isomers manual separations are carried out structure by two kinds of different colours light of color respectively under uviol lamp according to glow color difference
And performance test.
Product is characterized
1. Crystal Structure：
Structural characterization is carried out to single crystal samples using X-ray single crystal diffractometer.Details are as follows：Instrument is Brucker companies
Monocrystalline Apex Duo CCD x-ray diffractometers.X-ray source is Mo targets, wavelength 0.71073, graphite monochromator.Scanned with ω
Mode collects point diffraction, and data acquired is corrected through Lp, chooses I>The independent point diffraction of 2 σ (I) is used for ray crystallographic analysis.It is brilliant
The initial configuration of body and refine are completed using SHELX-97 structure elucidations program, and initial configuration pattern is solved with direct method, non-
The coordinate and anisotropic temperature factor of hydrogen atom carry out structure refinement using complete matrix least square method, the coordinate of hydrogen atom from
Geometric position is found out and is fixed, and its isotropic temperature factor participates in Structure Calculation, but is not involved in the refine of structure.Structure
The mathematic(al) representations such as the least square function, discrepancy factor, weight discrepancy factor, the weight factor that are used during analysis are as follows：
Least square function：
Temperature factor：
Discrepancy factor：
Weight discrepancy factor：
Weight factor：,
Crystal structure analysis display sample α-[(Cu4I4)L4] it is hexagonal crystal system, space group isR -3。β-[(Cu4I4)L4] it is list
Oblique system, space group isC2/c.They are presented classical Cu4I4Cube alkane structure, this cube of alkyl structure is four CuI3P tetra-
Face body by common prismatic into.Its actual crystal data, atomic coordinates and effective homogeneity displacement parameter, selection bond distance and key
Angle is shown in Table 1,2,3 respectively.
The crystallographic data of the Sample crystals structure of table 1
The α of table 2-[(Cu4I4)L4] atomic coordinates（×104）With effective homogeneity displacement parameter（Å2×103）
The β of table 3-[(Cu4I4)L4] atomic coordinates（×104）With effective homogeneity displacement parameter（Å2×103）
The α of table 4-[(Cu4I4)L4] selection bond distance（Å）And bond angle（°）
Symmetry transformations used to generate equivalent atoms: #1 -y+1,x-y,
z； #2 -x+y+1,-x+1,z
The β of table 5-[(Cu4I4)L4] selection bond distance（Å）And bond angle（°）
Symmetry transformations used to generate equivalent atoms: #1 -x,y,-z+1/
2
2. infrared spectrum characterization：
Examination of infrared spectrum, institute are carried out with ATR methods to sample using the infrared spectrometers of Perkin-Elmer Spectrum 2000
Obtain infrared spectrogram and see Fig. 1, each absworption peak of spectrogram and ownership are as shown in table 6.
The ultra-red vibration frequency of table 6 and ownership
| Ownership | |
| 3048 | |
| Phenyl ring stretching vibration | 1570,1389 |
| 1479 | |
| 1084,1009 | |
| 808 | |
| 738,698 |
Ultraviolet-ray visible absorbing：
The uv-visible absorption spectra test of sample is using the type UV/Vis spectrometers of Perkin-Elmer Lambda 800 in room
Temperature is lower to be determined, and its uv-visible absorption spectra is shown in Fig. 2.
From figure 2 it can be seen that sample has individual absworption peak at 340nm, this absworption peak comes from part three (4- chlorphenyls)
Phosphine ligands, corresponding electron transition is from the π-π * transition in respective ligand.
4. XRD powder diagrams：
Sample is tested using the XRD powder diffractometers from Rigaku Ultima, its 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)L4Before and after grinding, and β-
[(Cu4I4)L4] powder diagram after grinding with simulate the spectrogram that comes and be consistent substantially.Showing to realize can anti-phase
Become.
5. luminescent properties test：
Using the luminescent spectrum of Edinburgh Instrument F900 spectrometers test sample crystalline phase at different temperatures.
Emission spectra under Fig. 4 different temperatures.Under the excitation wavelength of 365nm, α-[(Cu4I4)L4] emission peak is
520nm, β-[(Cu4I4)L4It is 550nm.And the luminous of the compound has obvious temperature sensitivity matter：From 297K-77K,
With the reduction of temperature, luminous intensity gradually strengthens.When sample temperature recovers to room temperature, its fluorescence intensity is also restored back to come, can
See that it has reversible thermal stimulus response phenomenon.
6th, performance for stability test：
Chlorine atom in L=tri- (4- chlorphenyls) phosphine can form intramolecular and intermolecular hydrogen bonding as electron acceptor, so that material
The stability of material is greatly improved.And in L=tri- (4- anisyls) phosphine, C-O ehter bonds are weaker, material occurs to divide at a lower temperature
Solution.Therefore in this patent, the introducing of electron-withdrawing group is conducive to improving stability of material on phenyl ring.
Claims (3)
1. reversible force/heat that a kind of cuprous iodide/tri- (4- chlorphenyls) phosphine is constructed/solvent multiple stimulation responsive materials, its feature
It is that the molecular formula of cuprous iodide/tri- (4- chlorphenyls) phosphine is α-[(Cu4I4)L4] and β-[(Cu4I4)L4], L=tri-
(4- chlorphenyls) phosphine, its structure is four CuI3P tetrahedrons are by common prismatic into a cube of [(Cu for alkyl structure4I4)L4] cluster；
α- [(Cu4I4)L4] fluoresced green, its space group is six symmetrical sides highR-3；β-[(Cu4I4)L4] hair yellow fluorescence, it is empty
Between group be monoclineC 2/c。
2. reversible force/heat/solvent that a kind of cuprous iodide/tri- (4- chlorphenyls) phosphine according to claim 1 is constructed is multiple
Stimuli responsive material, it is characterised in that at room temperature, α-[(Cu4I4)L4] green fluorescence is sent under the irradiation of ultraviolet light, through grinding
Mill is changed into yellow fluorescence, and green fluorescence is returned to after acetonitrile is added dropwise；β-[(Cu4I4)L4] yellow fluorescence is issued in uviol lamp, grind
Fluorescence color keeps constant afterwards, and after acetonitrile is added dropwise, yellow fluorescence is changed into green fluorescence；With the reduction of temperature, two kinds of phases
Fluorescence intensity gradually strengthens.
3. one kind prepares reversible force/heat/solvent that cuprous iodide/tri- as claimed in claim 1 or 2 (4- chlorphenyls) phosphine is constructed
The method of multiple stimulation responsive materials, it is characterised in that synthetic method comprises the following steps：0.1mmol cuprous iodides are dissolved in 5
In mL acetonitriles, 0.1mmol tri- (4- chlorphenyls) phosphine is dissolved in 10 mL ethanol solutions, and both are mixed and stirred for, mistake after 10 min
Filter, gained clear liquid stands volatilization, colourless transparent crystal is obtained after 24h at room temperature, and crystal jaundice color is found after ultra violet lamp
With green two kinds of different colours light, different by two kinds of isomers manual separations according to glow color under uviol lamp, acquisition is described
Reversible force/heat/solvent multiple stimulation responsive materials.
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| CN108102639A (en) * | 2017-12-27 | 2018-06-01 | 内蒙古大学 | The anti-fake material preparation method that a kind of multiple optics signal by Spin transition regulation and control responds |
| 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 |
| CN109651408A (en) * | 2019-01-26 | 2019-04-19 | 济宁学院 | A kind of novel C uI complex and its preparation method and application |
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| CN115872975A (en) * | 2023-01-06 | 2023-03-31 | 暨南大学 | Cyclic trinuclear cuprous complex and preparation method and application thereof |
| 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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