CN114478628A - Application of tert-butyl pyrimidine triazole copper [ I ] dinuclear complex in stimulus response luminescent and photochromic material - Google Patents
Application of tert-butyl pyrimidine triazole copper [ I ] dinuclear complex in stimulus response luminescent and photochromic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 230000004044 response Effects 0.000 title claims abstract description 28
- CEWLDFUAIWSHIK-UHFFFAOYSA-N [Cu].N1N=NC=C1.C(C)(C)(C)C1=NC=CC=N1 Chemical compound [Cu].N1N=NC=C1.C(C)(C)(C)C1=NC=CC=N1 CEWLDFUAIWSHIK-UHFFFAOYSA-N 0.000 title claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 86
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 5
- 150000003852 triazoles Chemical class 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 12
- 229960001701 chloroform Drugs 0.000 abstract description 12
- 238000000227 grinding Methods 0.000 abstract description 12
- 230000009471 action Effects 0.000 abstract description 9
- -1 2-pyrimidyl Chemical group 0.000 abstract description 8
- 239000007787 solid Substances 0.000 description 39
- 238000004020 luminiscence type Methods 0.000 description 36
- 239000002245 particle Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 5
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- GHPAVFWNRVOJMJ-UHFFFAOYSA-N 2-(5-tert-butyl-1H-1,2,4-triazol-3-yl)pyrimidine Chemical compound CC(C)(C)c1n[nH]c(n1)-c1ncccn1 GHPAVFWNRVOJMJ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000004699 copper complex Chemical class 0.000 description 3
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBOQCPPINFMCBH-UHFFFAOYSA-N diphenylphosphane;methane Chemical compound C.C=1C=CC=CC=1PC1=CC=CC=C1.C=1C=CC=CC=1PC1=CC=CC=C1 SBOQCPPINFMCBH-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement 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
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- VZXWDGGSKPWCPO-UHFFFAOYSA-N pyrimidine;2h-triazole Chemical compound C1=CNN=N1.C1=CN=CN=C1 VZXWDGGSKPWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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- C07F9/28—Phosphorus compounds with one or more P—C bonds
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Abstract
The invention provides tert-butyl pyrimidine triazole copper [ I ]]Application of binuclear complex in stimulus-responsive luminescent and color-changing material, namely tert-butyl pyrimidine triazole copper [ I]The binuclear complex is perchlorate-bis [ 5-tert-butyl-3- [ 2-pyrimidyl)]-1H-1, 2, 4-triazole]Bis [ bis diphenylphosphinomethane]Hetero di-copper [ I ]]The molecular formula of the complex is as follows: c70H70Cl2Cu2N10O8P4The material belongs to a new stimulus-response luminescent color-changing material, has stimulus-response luminescent color-changing characteristics on mechanical grinding action, trichloromethane steam and dichloromethane steam, and has good application prospect.
Description
Technical Field
The invention relates to an application of tert-butyl pyrimidine triazole copper [ I ] dinuclear complex in a stimulus-response luminescent and color-changing material, belonging to the technical field of synthesis of new stimulus-response luminescent and color-changing materials.
Background
Due to the influence of strong spin-orbit coupling effect and heavy atom effect, the metal luminescent complex can theoretically utilize all energy from singlet state and triplet state, thereby effectively improving the luminous efficiency thereof. Currently, the metal luminescent complexes are mainly concentrated on the transition metals of the fifth and sixth periods, especially the transition metals of the VIII group, such as ruthenium, osmium, iridium and platinum. However, the transition metals of the fifth and sixth periods (except for a few metals of the first and second subgroups) are rare in the earth crust and difficult to extract, so the noble metal complex luminescent material has high use cost and causes the problem of shortage of raw materials after being applied in a large scale. In addition, the noble metal complexes are usually more toxic, especially the metal complexes such as ruthenium, osmium, rhenium and the like. Therefore, the large-scale application of the noble metal complex luminescent material not only can bring environmental pollution, but also can bring direct or indirect harm to production and users. The defects of high use cost, environmental unfriendliness and the like seriously restrict and prevent the large-scale application of the metal elements, so that the metal elements can be found out in the fifth and sixth periods.
Compared with the transition metals of the fifth period and the sixth period, the metal copper of the fourth period has rich resources, low price, excellent luminescence of the complex and environmental friendliness. In addition, the monovalent copper complex also has good room-temperature visible phosphorescence emission, and the luminescence of the monovalent copper complex can vary from ultraviolet to near infrared and covers the whole visible region. The monovalent copper luminescent complex has the advantages of rich resources, low price, excellent luminescence, environmental friendliness and the like, so that the monovalent copper luminescent complex has good potential application prospects in various fields such as luminescent devices, optical sensors, intelligent devices, anti-counterfeiting encryption and the like.
At present, the monovalent copper luminescent complexes reported in the literature are mostly monovalent copper mononuclear complexes. The monovalent copper polynuclear complex is more and more valued by people due to the advantages of novel structure, rich configuration, various coordination, excellent luminescence and the like. However, there are few reports on documents for constructing monovalent copper complex photochromic materials by combining azole-based polydentate ligands and organic diphosphine ligands, and particularly monovalent copper polynuclear complexes stimulate response to the photochromic materials.
The application of a pyrimidine triazole polydentate ligand [ 5-tert-butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole ] and an organic diphosphine ligand [ bis-diphenylphosphinomethane ] to design and synthesize a monovalent copper luminescent complex and use the monovalent copper luminescent complex as a stimulus-response luminescent and color-changing material is not disclosed in a literature report at present, and in conclusion, the application provides the application of a tert-butyl pyrimidine triazole copper [ I ] dinuclear complex in the stimulus-response luminescent and color-changing material to solve the problems.
Disclosure of Invention
In view of the above, one or more embodiments of the present disclosure are directed to an application of a t-butyl pyrimidine copper triazole [ I ] dinuclear complex in a stimulus-responsive photochromic material, so as to solve the problems mentioned in the background art.
In view of the above, one or more embodiments of the present disclosure provide a t-butylpyrimidine copper triazole [ I]The application of the binuclear complex in stimulus-responsive light-emitting and color-changing materials comprises the following steps: the tert-butyl pyrimidine triazole copper [ I ]]The double-core coordination compound stimulus response luminescent material is perchlorate bis [ 5-tert-butyl-3- [ 2-pyrimidyl ] photochromic material]-1H-1, 2, 4-triazole]Bis [ bis diphenylphosphinomethane]Hetero di-copper [ I ]]The molecular formula of the complex is as follows: c70H70Cl2Cu2N10O8P4The molecular weight is: 1501.26, the molecular structure is:
preferably, the perchlorate is bis [ 5-tert-butyl-3- [ 2-pyrimidinyl ]]-1H-1, 2, 4-triazole]Bis [ bis diphenylphosphinomethane]Hetero di-copper [ I ]]The crystal of the complex belongs to monoclinic system, P21Space group,/n, unit cell parameters: 14.204(2) and 14.152(2) respectively,
β＝93.560(5)°，
formula＝C70H70Cl2Cu2N10O8P4·2(CH2Cl2)，Z＝2，Mr＝1671.07，Dc＝1.420gcm-3，μ＝0.890mm-1，GOF＝1.057。
the invention also provides two preparation methods:
one method for preparing the tert-butyl pyrimidine triazole copper [ I ] dinuclear complex stimulus response luminescent and photochromic material comprises the following steps:
under argon atmosphere, the molar ratio of [ Cu [ CH ] is 1:1:13CN]4][ClO4]Bis (diphenylphosphinomethane) [ dppm for short ]]5-tert-butyl-3- [ 2-pyrimidinyl]-1H-1, 2, 4-triazole [ bpmtzH for short]Stirring and reacting in dichloromethane at normal temperature for 2-4 hr to obtain colorless transparent solution, evaporating the solvent under reduced pressure with rotary evaporator, and dissolving in dichloromethane-n-hexane mixed solvent at volume ratio of 1:10]Recrystallizing, filtering, recrystallizing to obtain colorless crystalline product, washing with diethyl ether for 3-4 times, and vacuum drying to obtain colorless solid product.
The second method for preparing the tertiary butyl pyrimidine triazole copper [ I ] dinuclear complex stimulus response luminescent and photochromic material comprises the following steps:
under the atmosphere of argon, the mole ratio of copper perchlorate [ Cu [ ClO ] hexahydrate is 1:5-10:2:24]2·6H2O]Excess copper powder, bis (diphenylphosphinomethane) (dppm for short)]5-tert-butyl-3- [ 2-pyrimidinyl]-1H-1, 2, 4-triazole [ bpmtzH for short)]In a mixed solvent of acetonitrile and dichloromethane (volume ratio of 1: 2)]Stirring at normal temperature for reaction for 2-4 hr, filtering, evaporating solvent under reduced pressure with rotary evaporator, and dissolving with dichloromethane-n-hexane mixture at volume ratio of 1:10]Recrystallizing, filtering, recrystallizing to obtain colorless crystalline product, washing with diethyl ether for 3-4 times, and vacuum drying to obtain colorless solid product.
From the above, it can be seen that the beneficial effects of the present invention are: the tertiary butyl pyrimidine triazole copper [ I ] dinuclear complex stimulus response luminescent color-changing material adopts 5-tertiary butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole and bis-diphenylphosphinomethane, and has the main purposes and meanings as follows: the polydentate ligand 5-tert-butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole with chelating function and the bidentate diphosphine ligand bis-diphenylphosphinomethane with bridging function are selected, and the method is mainly used for regulating and controlling the space stereoscopic effect, the electron density distribution and the N-H electronic characteristic of the copper [ I ] complex and realizing the reversible and controllable stimulus response luminescent and color changing performance of the copper [ I ] complex. At normal temperature, the maximum value of the luminescence wavelength of the copper [ I ] complex solid particles is 498nm, the luminescence life is 13 mus, and the luminescence quantum efficiency is 42%; after the solid particles are placed in a trichloromethane steam atmosphere, the maximum value of the luminescence wavelength of the solid particles is 486nm, the luminescence life is 15 mus, and the luminescence quantum efficiency is 31%; after the solid particles are placed in the methylene dichloride steam atmosphere again, the maximum value of the luminous wavelength of the solid particles is changed to 498nm again; the process is repeated and circulated continuously. This shows that the copper [ I ] complex luminescent material of the invention can generate photochromic property under the vapor of trichloromethane, and can recover the original luminescence under the vapor of dichloromethane, namely the copper [ I ] complex luminescent material of the invention has good selective response luminescent and photochromic properties for the vapor of trichloromethane and the vapor of dichloromethane. In addition, after the solid particles of the copper [ I ] complex are ground, the maximum value of the light-emitting wavelength of the solid powder is 512nm, the light-emitting lifetime is 10 mus, and the light-emitting quantum efficiency is 16%; after the ground solid powder is placed in a methylene dichloride steam atmosphere, the maximum value of the luminescence wavelength is 498nm, the luminescence life is 13 mus, and the luminescence quantum efficiency is 36%; grinding the solid powder again, and then changing the maximum value of the light-emitting wavelength of the solid powder into 512nm again; the maximum value of the light-emitting wavelength of the ground solid powder is changed into 498nm again after the ground solid powder is placed in the methylene dichloride steam atmosphere again; the process is repeated and circulated continuously. This shows that the copper [ I ] complex luminescent material of the present invention can generate photochromic properties under the action of mechanical grinding, and can recover the original luminescence under the action of dichloromethane vapor, that is, the copper [ I ] complex luminescent material of the present invention has stimulus response characteristics for both mechanical grinding and dichloromethane vapor. Therefore, the copper [ I ] complex luminescent material has the stimulation response characteristics to mechanical grinding action, trichloromethane steam and dichloromethane steam, and can be used for manufacturing elements of intelligent luminescent sensors capable of selectively responding and detecting the mechanical grinding action, the trichloromethane steam and the dichloromethane steam.
Drawings
In order to more clearly illustrate one or more embodiments or prior art solutions of the present specification, the drawings that are needed in the description of the embodiments or prior art will be briefly described below, and it is obvious that the drawings in the following description are only one or more embodiments of the present specification, and that other drawings may be obtained by those skilled in the art without inventive effort from these drawings.
FIG. 1 is a crystal structure diagram of a perchlorate-bis [ 5-tert-butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole ] & bis [ bis (diphenylphosphinomethane) copper [ I ] complex of the present invention.
FIG. 2 shows the solid state fluorescence emission spectrum of the perchlorate-bis [ 5-tert-butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole ]. bis [ bis (diphenylphosphinomethane ] copper [ I ] complex of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to specific embodiments.
It is to be noted that unless otherwise defined, technical or scientific terms used in one or more embodiments of the present specification should have the ordinary meaning as understood by those of ordinary skill in the art to which this disclosure belongs. The use of "first," "second," and similar terms in one or more embodiments of the specification is not intended to indicate any order, quantity, or importance, but rather is used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships may also be changed accordingly.
Examples
Referring to FIGS. 1 and 2, a tert-butyl pyrimidine triazole copper [ I ]]The application of the binuclear complex in the stimulus response luminescent and color-changing material is characterized by comprising the following steps: the tert-butyl pyrimidine triazole copper [ I ]]The binuclear complex stimulus-responsive luminescent and color-changing material is perchlorate-bis [ 5-tert-butyl-3- [ 2-pyrimidyl ] ester]-1H-1, 2, 4-triazole]Bis [ bis diphenylphosphinomethane]Hetero di-copper [ I ]]The molecular formula of the complex is as follows: c70H70Cl2Cu2N10O8P4The molecular weight is: 1501.26, the molecular structure is:
further, the perchlorate is bis [ 5-tert-butyl-3- [ 2-pyrimidyl ] ester]-1H-1, 2, 4-triazole]Bis [ bis diphenylphosphinomethane ]]Hetero di-copper [ I ]]The crystal of the complex belongs to monoclinic system, P21Space group,/n, unit cell parameters: 14.204(2) and 14.152(2) respectively,
β＝93.560(5)°，
formula＝C70H70Cl2Cu2N10O8P4·2(CH2Cl2)，Z＝2，Mr＝1671.07，Dc＝1.420gcm-3，μ＝0.890mm-1，GOF＝1.057。
the invention also provides two preparation methods:
one method for preparing the tert-butyl pyrimidine triazole copper [ I ] dinuclear complex stimulus response luminescent and photochromic material comprises the following steps:
under argon atmosphere, the molar ratio of [ Cu [ CH ] is 1:1:13CN]4][ClO4]Bis (diphenylphosphinomethane) [ dppm for short ]]5-tert-butyl-3- [ 2-pyrimidinyl]-1H-1, 2, 4-triazole [ bpmtzH for short]Stirring and reacting in dichloromethane at normal temperature for 2-4 hr to obtain colorless transparent solution, evaporating the solvent under reduced pressure with rotary evaporator, and dissolving in dichloromethane-n-hexane mixed solvent at volume ratio of 1:10]Recrystallizing, filtering, recrystallizing to obtain colorless crystalline product, washing with diethyl ether for 3-4 times, and vacuum drying to obtain colorless solid product.
The second method for preparing the tertiary butyl pyrimidine triazole copper [ I ] dinuclear complex stimulus response luminescent and photochromic material comprises the following steps:
under the atmosphere of argon, the mole ratio of copper perchlorate [ Cu [ ClO ] hexahydrate is 1:5-10:2:24]2·6H2O]Excess copper powder, bis (diphenylphosphinomethane) (dppm for short)]5-tert-butyl-3- [ 2-pyrimidinyl]-1H-1, 2, 4-triazole [ bpmtzH for short]In a mixed solvent of acetonitrile and dichloromethane (volume ratio of 1: 2)]Stirring at normal temperature for reaction for 2-4 hr, filtering, evaporating solvent under reduced pressure with rotary evaporator, and dissolving with dichloromethane-n-hexane mixture at volume ratio of 1:10]Recrystallizing, filtering, recrystallizing to obtain colorless crystalline product, washing with diethyl ether for 3-4 times, and vacuum drying to obtain colorless solid product.
The reaction mechanism adopted by the invention is as follows:
the method comprises the following steps:
the second method comprises the following steps:
the physical parameters of the obtained tert-butyl pyrimidine triazole copper [ I ] dinuclear complex stimulus response luminescent and color-changing material are as follows:
the molecular formula is as follows: c70H70Cl2Cu2N10O8P4
Molecular weight: 1501.26
Chinese name: perchlorate-bis [ 5-tert-butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole ] bis [ bis diphenylphosphinomethane ] copper (I) complex.
English name: [ Cu ]2[5-tert-butyl-3-(2-pyrimidinyl)-1H-1,2,4-triazole]2[bis(diphenylphosphino)meth ane]2][ClO4]2The abbreviation is: [ Cu ]2[bpmtzH]2[dppm]2][ClO4]2。
The following is illustrated by two specific examples:
example 1
Under argon atmosphere, [ Cu [ CH ]3CN]4][ClO4](33.0mg, 0.101mmol), bis-diphenylphosphinomethane (38.8mg, 0.101mmol) and 5-tert-butyl-3- [ 2-pyrimidinyl]Reacting (20.5mg, 0.101mmol) of (1H) -1,2, 4-triazole in 6mL of dichloromethane at normal temperature for 2 hours under stirring to obtain colorless transparent solution, evaporating the solvent under reduced pressure by using a rotary evaporator, and dissolving the solvent in a dichloromethane-n-hexane mixed solvent (the volume ratio is 1: 10)]Recrystallization was carried out, and the colorless crystalline product obtained by recrystallization was filtered, washed with ether 3 to 4 times, and dried in vacuo to give a colorless solid product (59.8mg, 0.040mmol, yield: 79%).
Calculated value of elemental analysis (C)70H70Cl2Cu2N10O8P4) Is as follows (%): c56.00, H4.70, N9.33; measured value: c56.03, H4.72, N9.30.
X-ray single crystal diffraction: the crystal belongs to monoclinic system, P21Space group,/n, unit cell parameters: 14.204(2), 14.152(2),
β＝93.560(5)°，
formula＝C70H70Cl2Cu2N10O8P4·2(CH2Cl2)，Z＝2，Mr＝1671.07，Dc＝1.420g cm-3，μ＝0.890mm-1GOF ═ 1.057, the crystal structure is shown in fig. 1.
The photoluminescence performance test result shows that the copper [ I ] dinuclear complex solid exhibits reversible and controllable stimulus response luminescence and color change performance at normal temperature. Under normal temperature, the maximum value of the luminescence wavelength of the copper [ I ] complex solid particles is 498nm, the luminescence life is 13 mus, and the luminescence quantum efficiency is 42%; after the solid particles are placed in a trichloromethane steam atmosphere, the maximum value of the luminescence wavelength of the solid particles is 486nm, the luminescence life is 15 mus, and the luminescence quantum efficiency is 31%; after the solid particles are placed in the methylene dichloride steam atmosphere again, the maximum value of the luminous wavelength of the solid particles is changed to 498nm again; the process is repeated and circulated continuously. In addition, after the solid particles of the copper [ I ] complex are ground, the maximum value of the light-emitting wavelength of the solid powder is 512nm, the light-emitting lifetime is 10 mus, and the light-emitting quantum efficiency is 16%; after the ground solid powder is placed in a methylene dichloride steam atmosphere, the maximum value of the luminescence wavelength is 498nm, the luminescence life is 13 mus, and the luminescence quantum efficiency is 36%; grinding the solid powder again, and then changing the maximum value of the light-emitting wavelength of the solid powder into 512nm again; the maximum value of the light-emitting wavelength of the ground solid powder is changed into 498nm again after the ground solid powder is placed in the methylene dichloride steam atmosphere again; the process is repeated and circulated continuously. The solid-state fluorescence emission spectrum is shown in FIG. 2.
Example 2
Under argon atmosphere, copper perchlorate [ Cu [ ClO ] hexahydrate4]2·6H2O](18.6mg, 0.050mmol) and excess copper powder (19.2mg, 0.302mmol) were reacted in 5mL acetonitrile at room temperature with stirring for 30 minutes, followed by addition of a solution of bis-diphenylphosphinomethane (38.5mg, 0.100mmol) in 10mL dichloromethane, reaction with stirring for 1 hour, and addition of 5-tert-butyl-3- [ 2-pyrimidinyl]Stirring and reacting-1H-1, 2, 4-triazole (20.3mg, 0.100mmol) at normal temperature for 2 hours, filtering, evaporating the solvent under reduced pressure by using a rotary evaporator, and mixing the solvent with dichloromethane (2mL) -n-hexane (20mL) at a volume ratio of 1:10]And (4) carrying out recrystallization. The colorless crystalline product obtained by recrystallization was filtered, washed 3-4 times with 12mL of diethyl ether and dried in vacuo to give the product as a colorless solid (54.6mg, 0.036mmol) in 72% yield.
The analytical characterization data are the same as in example 1.
The invention relates to a stimulus response luminescent color-changing material of tert-butyl pyrimidine triazole copper [ I ] binuclear complex, which selects 5-tert-butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole and bis-diphenylphosphine methane, and has the main purposes and meanings as follows: the polydentate ligand 5-tert-butyl-3- [ 2-pyrimidinyl ] -1H-1, 2, 4-triazole with chelating function and the bidentate diphosphine ligand bis-diphenylphosphinomethane with bridging function are selected, and the method is mainly used for regulating and controlling the space stereoscopic effect, the electron density distribution and the N-H electronic characteristic of the copper [ I ] complex and realizing the reversible and controllable stimulus response luminescent and color changing performance of the copper [ I ] complex. Under normal temperature, the maximum value of the luminescence wavelength of the copper [ I ] complex solid particles is 498nm, the luminescence life is 13 mus, and the luminescence quantum efficiency is 42%; after the solid particles are placed in a trichloromethane steam atmosphere, the maximum value of the luminescence wavelength of the solid particles is 486nm, the luminescence life is 15 mus, and the luminescence quantum efficiency is 31%; after the solid particles are placed in the methylene dichloride steam atmosphere again, the maximum value of the luminous wavelength of the solid particles is changed to 498nm again; the process is repeated and circulated continuously. This shows that the copper [ I ] complex luminescent material of the invention can generate photochromic property under the vapor of trichloromethane, and can recover the original luminescence under the vapor of dichloromethane, namely the copper [ I ] complex luminescent material of the invention has good selective response luminescent and photochromic properties for the vapor of trichloromethane and the vapor of dichloromethane. In addition, after the solid particles of the copper [ I ] complex are ground, the maximum value of the light-emitting wavelength of the solid powder is 512nm, the light-emitting lifetime is 10 mus, and the light-emitting quantum efficiency is 16%; after the ground solid powder is placed in a methylene dichloride steam atmosphere, the maximum value of the luminescence wavelength is 498nm, the luminescence life is 13 mus, and the luminescence quantum efficiency is 36%; grinding the solid powder again, and then changing the maximum value of the light-emitting wavelength of the solid powder into 512nm again; the maximum value of the light-emitting wavelength of the ground solid powder is changed into 498nm again after the ground solid powder is placed in the methylene dichloride steam atmosphere again; the process is repeated and circulated continuously. Research results show that the copper [ I ] complex luminescent material can generate photochromic property under the action of mechanical grinding and can recover the original luminescence under the action of dichloromethane vapor, namely the copper [ I ] complex luminescent material has the stimulus response characteristic to both mechanical grinding and dichloromethane vapor.
Therefore, the copper [ I ] complex luminescent material has the stimulation response characteristics to the mechanical grinding action, the trichloromethane steam and the dichloromethane steam, and can be used for manufacturing elements of intelligent luminescent sensors capable of selectively responding to and detecting the mechanical grinding action, the trichloromethane steam and the dichloromethane steam.
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (2)
1. Tert-butyl pyrimidine triazole copper [ I]The application of the binuclear complex in the stimulus response luminescent and color-changing material is characterized by comprising the following steps: the tert-butyl pyrimidine triazole copper [ I ]]The binuclear complex stimulus-responsive luminescent and color-changing material is perchlorate-bis [ 5-tert-butyl-3- [ 2-pyrimidyl ] ester]-1H-1, 2, 4-triazole]Bis [ bis diphenylphosphinomethane]Hetero di-copper [ I ]]The molecular formula of the complex is as follows: c70H70Cl2Cu2N10O8P4The molecular weight is: 1501.26, the molecular structure is:
2. the tert-butyl pyrimidine triazole copper [ I ] according to claim 1]The application of the binuclear complex in stimulus-responsive light-emitting and color-changing materials is characterized in that the perchlorate-bis [ 5-tert-butyl-3- [ 2-pyrimidyl ] amine]-1H-1, 2, 4-triazole]Bis [ bis diphenylphosphinomethane]Hetero di-copper [ I ]]The crystal of the complex belongs to a monoclinic system, P21Space group,/n, unit cell parameters: a is 14.204(2), b is 14.152(2)，
β＝93.560(5)°，
formula＝C70H70Cl2Cu2N10O8P4·2(CH2Cl2)，Z＝2，Mr＝1671.07，Dc＝1.420g cm-3，μ＝0.890mm-1，GOF＝1.057。
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| CN106349258A (en) * | 2016-08-25 | 2017-01-25 | 江西理工大学 | Pyridyl triazole copper [I] complex organic vapor luminescent photochromic material and preparation method |
| CN106432290A (en) * | 2016-09-29 | 2017-02-22 | 江西理工大学 | Tert-butyl pyrimidine triazole copper [I] dinuclear complex luminescent material and preparation method thereof |
| CN111909183A (en) * | 2020-08-28 | 2020-11-10 | 江西理工大学 | Preparation method of tert-butyl pyridine pyrazole copper [ I ] dinuclear complex stimulus response luminescent and photochromic material |
| CN111961078A (en) * | 2020-08-28 | 2020-11-20 | 江西理工大学 | Preparation method of trifluoromethyl pyridine pyrazole copper [ I ] dinuclear complex stimulus response luminescent and photochromic material |
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| CN106349258A (en) * | 2016-08-25 | 2017-01-25 | 江西理工大学 | Pyridyl triazole copper [I] complex organic vapor luminescent photochromic material and preparation method |
| CN106432290A (en) * | 2016-09-29 | 2017-02-22 | 江西理工大学 | Tert-butyl pyrimidine triazole copper [I] dinuclear complex luminescent material and preparation method thereof |
| CN111909183A (en) * | 2020-08-28 | 2020-11-10 | 江西理工大学 | Preparation method of tert-butyl pyridine pyrazole copper [ I ] dinuclear complex stimulus response luminescent and photochromic material |
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