CN107793438B - A kind of copper (I) phosphine benzene heterocycle complex and its preparation method and application - Google Patents
A kind of copper (I) phosphine benzene heterocycle complex and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 95
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 95
- 239000010949 copper Substances 0.000 claims description 48
- 229910004856 P—O—P Inorganic materials 0.000 claims description 43
- 239000003446 ligand Substances 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- DDGIHXFDWLCKRZ-UHFFFAOYSA-N 4,6-diphenylpyran-2-one Chemical compound O1C(=O)C=C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 DDGIHXFDWLCKRZ-UHFFFAOYSA-N 0.000 claims description 4
- UYAADBLIRXSMHB-UHFFFAOYSA-N C1(=CC=CC=C1)PC1=CC=CC=C1.[Cl] Chemical compound C1(=CC=CC=C1)PC1=CC=CC=C1.[Cl] UYAADBLIRXSMHB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000002240 furans Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000003780 insertion Methods 0.000 claims 1
- 230000037431 insertion Effects 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 11
- -1 copper (I) metal complex Chemical class 0.000 abstract description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 18
- 238000002189 fluorescence spectrum Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 235000004237 Crocus Nutrition 0.000 description 3
- 241000596148 Crocus Species 0.000 description 3
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- AXEPYENIMXTQSM-UHFFFAOYSA-N benzene;phosphane Chemical compound P.C1=CC=CC=C1 AXEPYENIMXTQSM-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 2
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- YBVPWLHQQWQJAR-UHFFFAOYSA-N [Cl+].[Cu+] Chemical compound [Cl+].[Cu+] YBVPWLHQQWQJAR-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- OAFXFZNYKPMZBJ-UHFFFAOYSA-N copper(1+);phosphane Chemical compound P.[Cu+] OAFXFZNYKPMZBJ-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical compound C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HKCRVXUAKWXBLE-UHFFFAOYSA-N terbium(3+) Chemical compound [Tb+3] HKCRVXUAKWXBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/32—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in transmittance, scattering or luminescence in optical fibres
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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
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Abstract
The invention discloses a kind of copper (I) phosphine benzene heterocycle complexs and its preparation method and application.The structural formula of copper (I) the phosphine benzene heterocycle complex is shown in formula I:, wherein X is halogen.The complex can show good phosphorescence performance with 77K at room temperature, and the service life at room temperature is 100 microseconds, and the 77K lower service life is up to 2 milliseconds or so, and within the scope of 77K~297K, which has the dependence of height to temperature；Its service life of sensor made of the complex has the linear dependence of height to temperature, and has excellent sensitivity and stability, and has very wide temperature-responsive range 77K~337K；Present invention firstly discloses copper (I) metal complex fluorescent temperature sensor with intuitive temperature Yu service life linear relationship, have many advantages, such as at low cost, prepares simple, possess great application prospect.
Description
Technical field
The invention belongs to material chemistry technical fields, and in particular, to a kind of copper (I) phosphine benzene heterocycle complex and its preparation
Methods and applications.
Background technique
In various fields, temperature is all a crucial characteristic parameter.Temperature sensor, as what is grown up earliest
Type device abundant, in meteorology, aeronautics, scientific research, the fields such as industry have to be widely applied very much.And metal combination
Object fluorescence temperature sensor has obtained extensive research and development with its distinctive property.They usually have service life of Microsecond grade,
It absorbs in visible range, emits fluorescence or phosphorescence, and there is very big Stokes shift.And these metal complexs point
Sub- probe usually has certain susceptibility to oxygen, and membrane material is made applied to fluorescence temperature so being typically embedded in high polymer
In terms of probe.Currently, studying more fluorescence temperature complex is rubidium (III), iridium (III), the noble metals such as platinum (II) mostly
And europium (III), terbium (III) wait rare earth metals (Wang, X.-d.; Wolfbeis, O. S.; Meier, R. J.,
Chem. Soc. Rev. 2013,42 (19), 7834-7869).However, such small molecule metal complex being reported
The available temperature range of fluorescence temperature sensor is usually from 297 K of room temperature to 350 K of high temperature or so, and application range is probably 70
K or so is lower than 100 K mostly, and the sensor that can be used for low temperature is very few.Most of sensor life-time varies with temperature
Sensitivity less than 5 μ s/K, (Liebsch, G.; Klimant, I.; Wolfbeis, O. S., Adv. Mater.
1999,11(15), 1296-1299；Borisov, S. M.; Vasylevska, A. S.; Krause, C.;
Wolfbeis, O. S., Adv. Funct. Mater. 2006,16 (12), 1536-1542；Fischer, L. H.;
Stich, M. I. J.; Wolfbeis, O. S.; Tian, N.; Holder, E.; Schäferling, M.,
Chem. Eur.J. 2009,15 (41), 10857-10863；Zelelow, B.; Khalil, G. E.; Phelan,
G.; Carlson, B.; Gouterman, M.; Callis, J. B.; Dalton, L. R., Sens.Actuators,
B: 2003,96 (1–2), 304-314；Katagiri, S.; Hasegawa, Y.; Wada, Y.; Yanagida, S.,
Chem. Lett. 2004,33 (11), 1438-1439；Yu, J.; Sun, L.; Peng, H.; Stich, M. I.
J., J. Mater. Chem. 2010,20 (33), 6975-6981).So research is more highly sensitive, temperature range is wide
And the sensor that can be used for more low temperature has certain practical significance.
In addition, currently, noble metal used in existing sensor and rare earth metal comparatively price is relatively high, lead to fluorescence temperature
Spend the higher cost of sensor.As temperature sensor development is increasingly mature, product cost is also an important factor.Metal
Copper complex, which is applied to fluorescence temperature sensor, can solve the problem.Metallic copper is cheap and easily-available, and according to the literature, copper (I)
Metal complex is demonstrated by excellent luminescent properties, there is very big application prospect in terms of fluorescence temperature sensor.
Steffen in 2014, M ü ller et al. report it is a kind of containing phosphine benzene heterocycle with the big steric hindrance of large-substituent
Cu4Br4Cluster complex, intensity and service life are gradually increased with the reduction of temperature, this work is that first case is reported at room temperature still
Show the complex of phosphorescence.Currently, being also very rare about such copper (I) complex report containing phosphine benzene heterocycle
(P. Roesch, J. Nitsch, M. Lutz, J. Wiecko, A. Steffen, C. M ü ller,Inorganic Chemistry 2014, 53, 9855-9859).Service life of the complex under room temperature and 77K is respectively 171 microseconds and 1516
Microsecond not only has the service life more higher than other complexs at room temperature, but also lifetime change is very big within this temperature range,
Introducing big steric group makes the complex have the long-life.Therefore matched based on the phosphorescence copper (I) that intensity and service life vary with temperature
Closing object and manufactured temperature sensor is material a kind of very novel and with development potentiality.Recently, the present inventor team
A kind of copper (I) complex with phosphine benzene heterocycle biphosphine ligand is reported, such complex equally has the service life (X. of Microsecond grade
Chen, Z. Li, F. Yanan, H. Gr ü tzmacher, Eur. J. Inorg. Chem.2016,562-562).But
It is that the average life span of such complex at room temperature only has 20 microseconds, and lifetime change is not within the scope of room temperature and 77K
It is obvious that so having certain limitation in terms of as fluorescence temperature sensor.
Summary of the invention
The technical problem to be solved by the present invention is to overcome fluorescence temperature sensor sensitivity in the prior art low, temperature model
Narrow, fluorescence intensity and service life can not vary with temperature defect and deficiency are enclosed, a kind of phosphine benzene with excellent luminance performance is provided
Double phosphine copper (I) complexs of heterocycle, under room temperature and low temperature, the service life is respectively 100 microseconds and 2 milliseconds or so, can be emitted
The phosphorescence of crocus out；And its luminous intensity and service life can increase with the reduction of temperature, with height temperature according to
Lai Xing can be used as fluorescence probe and be applied to prepare fluorescence temperature sensor, the hair of prepared fluorescence temperature sensor
The features such as good linear relationship is presented in luminous intensity and service life and temperature, and has high sensitivity, the wide range of linearity.
The object of the present invention is to provide a kind of copper (I) phosphine benzene heterocycle complexs.
It is a further object of the present invention to provide the preparation method of above-mentioned copper (I) phosphine benzene heterocycle complex and its in fluorescence temperature
Application in terms of sensor.
Another object of the present invention, which is to provide, prepares fluorescence temperature sensor using above-mentioned copper (I) phosphine benzene heterocycle complex
Method.
Above-mentioned purpose of the invention is to give realization by the following technical programs:
A kind of copper (I) phosphine benzene heterocycle complex, is named as [(phen)2C5P-O-P(phen)2]2[Cu2X2], structural formula
It is shown in formula I:
；Wherein, X is halogen.
The present invention increases steric hindrance, obtains a kind of intensity and service life with temperature by adding big substituent group on phosphine benzene heterocycle
Spend the complex of variation.Copper (I) the cluster center of the complex is two halogen atom bridgings, two copper atoms, forms a double-core
Cu2X2Quadrangular ring-shaped structure, two copper atoms are separately connected two phosphorus atoms of a ligand.
Preferably, the halogen is Cl, Br or I, i.e. gained copper (I) phosphine benzene heterocycle complex is respectively copper (I) chlorine
The double phosphine compositions of phosphine benzene heterocycle, the double phosphine compositions of copper (I) bromine phosphine benzene heterocycle and the double phosphine compositions of copper (I) iodine phosphine benzene heterocycle.
The preparation method of above-mentioned copper (I) phosphine benzene heterocycle complex, includes the following steps:
S1. in an inert atmosphere, by 4,6- diphenyl -2- pyranone, [Na (OCP) (dioxane)2.5] and anhydrous four
Hydrogen furans is added in reaction vessel and is heated to reflux 12~36 hours (preferably 24 hours).It is cooling, filtering, successively with anhydrous tetrahydro furan
It mutters, anhydrous ether extraction, anhydrous n-hexane washing obtains intermediate product (phen)2C5PONa；
S2. in an inert atmosphere, the intermediate product and diphenylphosphine chlorine step S1 obtained, reaction, which is added, in dry toluene holds
It in device, is stirred at room temperature 2~6 hours (preferably 4 hours), filters, ligand (phen) is obtained after filtrate is drained2C5P-O-P
(phen)2；
S3. in an inert atmosphere, the ligand that step S2 is obtained is reacted 1~3 with cuprous salt CuX in anhydrous tetrahydro furan
Hour (preferably 2 hours), filtering obtain solid, then wash solid with anhydrous n-hexane to get complex [(phen) is arrived2C5P-
O-P(phen)2]2[Cu2X2]；Wherein, X is halogen.
Preferably, the inert atmosphere is nitrogen or argon gas.
Preferably, the halogen is Cl, Br or I.
Preferably, 4,6- diphenyl -2- pyranone described in step S1 and [Na (OCP) (dioxane)2.5] mole ratio
Are as follows: 1~1.2:1.
Preferably, intermediate product (phen) described in step S22C5The mole ratio of PONa and diphenylphosphine chlorine are as follows: 1~1.2:
1。
Preferably, ligand (phen) described in step S32C5P-O-P(phen)2With the mole ratio of cuprous salt CuX are as follows: 1~
1.2:1.
Above-mentioned copper (I) phosphine benzene heterocycle complex of the present invention has excellent luminescent properties, under room temperature and low temperature, longevity
Life is respectively 100 microseconds and 2 milliseconds or so, can launch the phosphorescence of crocus；Its luminous intensity and service life can be with temperature
The reduction of degree and increase, with height temperature dependency, can be used as fluorescence probe be applied to prepare fluorescence temperature biography
Sensor.
Therefore, above-mentioned copper (I) phosphine benzene heterocycle complex as or preparation temperature sensor in terms of application also in this hair
In bright protection scope.The application is based primarily upon fluorescence intensity and service life to temperature high dependency.
Preferably, the temperature sensor is fluorescence temperature sensor.
It is highly preferred that the fluorescence temperature sensor is a kind of temperature sensor that metal complex is embedded in high-polymer membrane.
Particularly preferably, the application is to pass copper (I) phosphine benzene heterocycle complex for fluorescence temperature as fluorescence probe
Sensor.
It is by above-mentioned copper (I) phosphine benzene heterocycle complex [(phen) the present invention also provides a kind of fluorescence temperature sensor2C5P-O-P(phen)2]2[Cu2X2] it is embedded in the fluorescence temperature sensor film being prepared into high polymer.
Specifically by above-mentioned copper (I) phosphine benzene heterocycle complex [(phen)2C5P-O-P(phen)2]2[Cu2X2] He Gaoju
Object is dissolved in n,N-Dimethylformamide, stirs 6~10 hours (preferably 8 hours), and it is small to heat 3~6 for spin coating in an inert atmosphere
When (preferably 4.5 hours), coordination compound film [(phen) can be obtained2C5P-O-P(phen)2]2[Cu2Cl2]@PAN。
Preferably, the complex [(phen)2C5P-O-P(phen)2]2[Cu2X2] it with the mass ratio of high polymer is 1:100
~150.
Most preferably, the complex [(phen)2C5P-O-P(phen)2]2[Cu2X2] with the mass ratio of high polymer it is 1:
110。
Preferably, the high polymer is polyacrylonitrile.In conclusion copper (I) phosphine benzene heterocycle complex of the invention is in room
Temperature is lower and 77K can show good phosphorescence performance.Service life at room temperature is 100 microseconds, and the 77K lower service life is up to 2
Millisecond or so.Within the scope of 77K~297K, all complex service life have the dependence of height to temperature, and have higher
Sensitivity, therefore can be used for preparing fluorescence temperature sensor.Such complex is embedded in polymer polyacrylonitrile, is obtained
A kind of fluorescence temperature sensor film.Its service life of sensors with auxiliary electrode has the linear dependence of height to temperature, and has excellent
Sensitivity, it is often more important that, with very wide temperature-responsive range 77K~337K, which is higher than report at present
Other micromolecular metal combination species temperature sensors.With regard to it is currently understood that this is first kind report for the research work arrived
Copper (I) the metal complex fluorescent temperature sensor with intuitive temperature and service life linear relationship in road.And compared to other
Metal complexes temperature sensor, the metallic copper is cheap and easily-available, so sensors with auxiliary electrode has great application prospect.
Compared with prior art, the invention has the following beneficial effects:
(1) copper (I) phosphine benzene heterocycle complex of the present invention has excellent luminosity, under room temperature and low temperature,
Service life is respectively 100 microseconds and 2 milliseconds or so, can launch the phosphorescence of crocus, and luminous intensity and service life can be with
The reduction of temperature and increase, with height temperature dependency, can be used as fluorescence probe applied to fluorescence temperature sensing
It is the good material for preparing fluorescence temperature sensor in terms of device.
(2) fluorescence temperature sensor that the present invention is prepared reaches 1.5 milliseconds or so in the service life of room temperature, emits orange
The phosphorescence of color, with the reduction of temperature, luminous intensity and service life and temperature are presented good linear relationship, temperature use scope from
77K to 337K is up to 260K, and has very high sensitivity.
(3) the sensor phase of copper of the invention (I) phosphine benzene heterocycle complex fluorescent temperature sensor and existing same type
Than there is very big temperature use scope, and there is very high sensitivity.
(4) ligand used in copper (I) complex of the present invention is the biphosphine ligand of the very novel heterocycle of benzene containing phosphine, and first
It is secondary to obtain a kind of copper (I) metal complex fluorescent temperature sensor with intuitive temperature Yu service life linear relationship.
(5) copper (I) metal complex fluorescent temperature sensor of the present invention is at low cost compared with other temperature sensors, preparation
Simply.
Detailed description of the invention
Fig. 1 is complex [(phen)2C5P-O-P(phen)2]2[Cu2X2] route of synthesis.
Fig. 2 is the X-Ray crystal structure of complex；A is [(phen)2C5P-O-P(phen)2]2[Cu2Cl2], B is
[(phen)2C5P-O-P(phen)2]2[Cu2Br2]。
Fig. 3 is ligand (phen)2C5P-O-P(phen)2With complex [(phen)2C5P-O-P(phen)2]2[Cu2X2] purple
Outer abosrption spectrogram.
Fig. 4 is complex [(phen)2C5P-O-P(phen)2]2[Cu2Cl2] fluorescence spectra.
Fig. 5 is complex [(phen)2C5P-O-P(phen)2]2[Cu2Br2] fluorescence spectra.
Fig. 6 is complex [(phen)2C5P-O-P(phen)2]2[Cu2I2] fluorescence spectra.
Fig. 7 is fluorescence temperature sensor film [(phen)2C5P-O-P(phen)2]2[Cu2Cl2]@PAN fluorescence spectra.
Fig. 8 is fluorescence temperature sensor film [(phen)2C5P-O-P(phen)2]2[Cu2Br2]@PAN fluorescence spectra.
Fig. 9 is fluorescence temperature sensor film [(phen)2C5P-O-P(phen)2]2[Cu2I2]@PAN fluorescence spectra.
Specific embodiment
The present invention is made with specific embodiment with reference to the accompanying drawings of the specification and further being elaborated, the embodiment
It is served only for explaining the present invention, be not intended to limit the scope of the present invention.Test method as used in the following examples is such as without spy
Different explanation, is conventional method；Used material, reagent etc., unless otherwise specified, for the reagent commercially obtained
And material.
The preparation of the double phosphine compositions of 1 bronze medal of embodiment (I) chlorine phosphine benzene heterocycle
1, ligand is prepared
(1) under nitrogen atmosphere, by (2.0g, 8.0mmol) 4,6- diphenyl -2- pyranone, (2.43 g, 8.0 mmol)
[Na(OCP)·(dioxane)2.5] and 50mL anhydrous tetrahydro furan be added reaction flask in 90 DEG C be heated to reflux 24 hours.Reaction
After, anhydrous tetrahydro furan, anhydrous ether extraction are successively used in cooling, filtering, and anhydrous n-hexane washs solid, are obtained corresponding
Intermediate product be faint yellow solid powder (phen)2C5PONa.Yield: 73%.185 DEG C of fusing point.1H NMR (CD3CN, 400
MHz): δ = 7.65 (d, 4 H, Carom), 7.37 (t, 2 H, Carom), 7.29 (m, 5 H, Carom&C5),
7.00 (d, 1 H, C5); 13C{1H}NMR (CD3CN, 100.5 MHz): δ =209.5 (d, C5), 171.5 (d,
C5), 145.8(d, C5) 145.2(s, C5), 144.2(s, C5), 128.8(d, Carom), 127.6(s, Carom),
127.3 (d, Carom), 127.1(d, Carom), 122.2(d, Carom), 119.2 (d, Carom). 31P{1H} NMR
(CD3CN, 161.9 MHz) δ = 140.5。
(2) under nitrogen atmosphere, the intermediate product (400 mg, 1.40 mmol) (phen) step (1) obtained2C5PONa
With (308 mg, 1.40 mmol) diphenylphosphine chlorine, 10 ml dry toluenes are added in reaction flask, are stirred at room temperature 4 hours, filter,
Filtrate is obtained, is drained, ligand (phen) can be obtained2C5P-O-P(phen)2.Yield: 97%.1H NMR (C6D6, 400
MHz): δ = 7.86 (m, 2 H, C5), 7.73 (m, 4 H, Carom), 7.53 (d, 2 H, Carom), 7.34
(d, 2 H, Carom), 7.10 (m,12 H, Carom); 13C{1H}NMR (C6D6, 100.5 MHz): δ = 192.2
(dd, C5), 170.0(dd, C5), 145.6 (d, C5), 143.6 (d, C5), 140.6(d, C5), 140.5 (d,
Carom), 131.0(d, Carom), 129.8 (s, Carom), 128.6 (dd, Carom), 127.9 (s, Carom),
127.7 (s, Carom), 127.4 (s, Carom), 123.5 (t, Carom); 31P{1H} NMR (C6D6, 161.9 MHz)
δ = 144 (d, 1 J PP = 113.3 Hz, phosphinine - P), 114 (d, 1 J PP = 113.3 Hz,
diphenylphosphine - P)。
2, the double phosphine compositions of copper (I) chlorine phosphine benzene heterocycle are prepared
Under nitrogen atmosphere, by ligand obtained above (140 mg, 0.31 mmol) (phen)2C5P-O-P(phen)2With
(30.7 mg, 0.31 mmol) stannous chloride CuCl reacts 2 hours in anhydrous tetrahydro furan, and filtering obtains solid, use is anhydrous
N-hexane washs solid to get complex 1:[(phen is arrived)2C5P-O-P(phen)2]2[Cu2Cl2].Yield: 86%.
Anal. Calcd for C58H44P4O2Cu2Cl2: C, 63.63%；H, 4.05%；Found:C, 62.07%, 3.93
%.
UV/Vis:λ1 = 322 nm, λ2 = 410 nm.
IR (ATR, [cm-1]): 3058 (w, C-H str.), 1966 (w), 1900 (w), 1822 (w),
1777 (w),1571 (m), 1530, 1493, 1475, 1450 (m, - C6H5), 1437 (m), 1384 (m),
1353 (w), 1335 (w), 1312 (w), 1273 (w), 1251 (w), 1183 (w), 1139 (s, C-O
str.), 1108 (s), 1079 (m), 1027 (w), 999 (w), 957 (s), 915 (w), 898 (w), 883
(m), 871 (m), 794 (m), 759 (s), 742 (m), 727 (m), 703 (s), 690 (ss).
The preparation of the double phosphine compositions of 2 bronze medal of embodiment (I) bromine phosphine benzene heterocycle
Ligand (phen)2C5P-O-P(phen)2Prepare it is same as Example 1, under nitrogen atmosphere, by ligand (18.6
Mg, 0.13 mmol) (phen)2C5P-O-P(phen)2With (58.0 mg, 0.13 mmol) cuprous bromide CuBr in anhydrous tetrahydro
It is reacted 2 hours in furans, filters, obtain solid, wash solid with anhydrous n-hexane to get complex 2:[(phen is arrived)2C5P-
O-P(phen)2]2[Cu2Br2].Yield: 87%.
Anal. Calcd for C58H44P4O2Cu2Br2: C, 58.85%；H, 3.75%；Found:C, 58.82%；H,
3.88 %.
UV/Vis: λ1 = 328 nm, λ2 = 410 nm.
IR (ATR, [cm-1]): 3057 (w, C-H str.), 1965 (w), 1900 (w), 1814 (w),
1777 (w), 1570 (m), 1531, 1492, 1472, 1450 (m, -C6H5), 1436 (m), 1383 (m),
1353 (w), 1334 (w), 1312 (w), 1272 (w), 1249 (w), 1184 (w), 1138 (s, C-O
str.), 1107 (s), 1079 (m), 1027 (w), 999 (w), 957 (s), 915 (w), 898 (w), 883
(m), 871 (m), 794 (m), 759 (s), 742 (m), 727 (m), 704 (s), 690 (ss).
The preparation of the double phosphine compositions of 3 bronze medal of embodiment (I) iodine phosphine benzene heterocycle
Ligand (phen)2C5P-O-P(phen)2Prepare it is same as Example 1, under nitrogen atmosphere, by ligand (13.6
Mg, 0.07 mmol) (phen)2C5P-O-P(phen)2With (32.0 mg, 0.07 mmol) cuprous iodide CuI in anhydrous tetrahydro furan
Mutter it is middle reaction 2 hours, filtering, obtain solid, with anhydrous n-hexane wash solid to get arrive complex 3:[(phen)2C5P-O-P
(phen)2]2[Cu2I2].Yield: 90%.
Anal. Calcd for C58H44P4O2Cu2I2: C, 54.52%；H, 3.47%；Found:C, 54.21%, H, 3.45
%.
UV/Vis: λ1 = 332 nm, λ2 = 410 nm.
IR (ATR, [cm-1]): 3054 (w, C-H str.), 1956 (w), 1900 (w), 1817 (w),
1776 (w), 1570 (m), 1532, 1492, 1471, 1450 (m, -C6H5), 1436 (m), 1381 (m),
1353 (w), 1334 (w), 1313 (w), 1271 (w), 1248 (w), 1185 (w), 1135 (s, C-O
str.), 1107 (s), 1079 (m), 1068 (w), 1028 (w), 999 (w), 957 (s), 917 (w), 899
(w), 883 (m), 871 (m), 791 (m), 759 (s), 742 (m), 727 (m), 701 (s), 690 (ss).
4 complex of embodiment [(phen)2C5P-O-P(phen)2]2[Cu2Cl2] and [(phen)2C5P-O-P(phen)2]2
[Cu2Br2] X-Ray crystal structure measurement
By the measurement of crystal structure, shown in result figure 2, in two, copper cluster center, two copper of halogen bridging of such ligand
The heart forms Cu2X2Double-core planar structure.
5 ligand of embodiment (phen)2C5P-O-P(phen)2With complex [(phen)2C5P-O-P(phen)2]2[Cu2X2]
The measurement of ultra-violet absorption spectrum
By the measurement of ultraviolet spectra, as a result as shown in figure 3, such complex has, there are two ultraviolet absorption bands, for institute
Have for complex, one of absorption band is respectively in 322 nm, 328 nm and 332 nm.Another absorption band is 410
nm.And for ligand, it is not absorbed by force near 410 nm, two absorption bands are respectively 301 nm and 346 nm.This says
The bright absorption band observed near 410 nm derives from the electric charge transfer of ligand and copper cluster center.
6 complex of embodiment [(phen)2C5P-O-P(phen)2]2[Cu2Cl2] fluorescence spectrum measurement
By to complex [(phen)2C5P-O-P(phen)2]2[Cu2Cl2] carry out fluorescence spectrum measurement, result figure 4
Shown, the excitation wavelength of the complex is 410 nm, and launch wavelength is 692 nm.Within the scope of 77 K to 297 K, fluorescence intensity
Reduce as the temperature rises with the service life.It is respectively 144.4 and 2317.9 μ s in 77 K and 297 K service life.
7 complex of embodiment [(phen)2C5P-O-P(phen)2]2[Cu2Br2] fluorescence spectrum measurement
By to complex [(phen)2C5P-O-P(phen)2]2[Cu2Br2] carry out fluorescence spectrum measurement, as a result as scheme
Shown in 5, the excitation wavelength of the complex is 410 nm, and launch wavelength is 690 nm.Within the scope of 77 K to 297 K, fluorescence is strong
Degree and service life reduce as the temperature rises.It is respectively 266.6 and 1868.4 μ s in 77 K and 297 K service life.
8 complex of embodiment [(phen)2C5P-O-P(phen)2]2[Cu2I2] fluorescence spectrum measurement
By to complex [(phen)2C5P-O-P(phen)2]2[Cu2I2] measurement that carries out fluorescence spectrum, as a result such as Fig. 6
Shown, the excitation wavelength of the complex is 410 nm, and launch wavelength is 684 nm.Within the scope of 77 K to 297 K, fluorescence intensity
Reduce as the temperature rises with the service life.It is respectively 63.8 and 388.4 μ s in 77 K and 297 K service life.
The preparation of the double phosphine composition fluorescence temperature sensors of 9 cupric of embodiment (I) phosphine benzene heterocycle
Copper (I) complex [(phen) prepared by Examples 1 to 32C5P-O-P(phen)2]2[Cu2X2] (0.5 mg) and
Polymer polyacrylonitrile (55mg) is dissolved in n,N-Dimethylformamide (1 mL).Stirring 8 hours, the spin coating in nitrogen atmosphere.
It is placed in thermal station and heats 4.5 hours, coordination compound film [(phen) can be obtained2C5P-O-P(phen)2]2[Cu2X2]@PAN。
10 fluorescence temperature sensor of embodiment [(phen)2C5P-O-P(phen)2]2[Cu2Cl2]@PAN fluorescence spectrum survey
It is fixed
By fluorometric investigation, as a result as shown in fig. 7, the excitation wavelength of the sensor is 370 nm, launch wavelength 590
nm.Within the scope of 77 K to 337 K, fluorescence intensity and service life reduce as the temperature rises, and variation with temperature is in
Now simple linear relationship, service life sensitivity reach 6.99 μ s/K.
11 fluorescence temperature sensor of embodiment [(phen)2C5P-O-P(phen)2]2[Cu2Br2]@PAN fluorescence spectrum survey
It is fixed
By fluorometric investigation, as a result as shown in figure 8, the excitation wavelength of the sensor is 370 nm, launch wavelength 600
nm.Within the scope of 77 K to 337 K, fluorescence intensity and service life reduce as the temperature rises, and variation with temperature is in
Now simple linear relationship, service life sensitivity reach 4.46 μ s/K.
12 fluorescence temperature sensor of embodiment [(phen)2C5P-O-P(phen)2]2[Cu2I2]@PAN fluorescence spectrum survey
It is fixed
By fluorometric investigation, as a result as shown in figure 9, the excitation wavelength of the sensor is 370 nm, launch wavelength 600
nm.Within the scope of 77 K to 337 K, fluorescence intensity and service life reduce as the temperature rises, and variation with temperature is in
Now simple linear relationship, service life sensitivity reach 3.71 μ s/K.
Claims (10)
1. a kind of copper (I) phosphine benzene heterocycle complex, which is characterized in that its structural formula is shown in formula I:
；Wherein, X is halogen.
2. copper (I) phosphine benzene heterocycle complex according to claim 1, which is characterized in that the halogen be Cl, Br or
I。
3. the preparation method of copper (I) phosphine benzene heterocycle complex of any of claims 1 or 2, which is characterized in that including walking as follows
It is rapid:
S1. in an inert atmosphere, by 4,6- diphenyl -2- pyranone, [Na (OCP) (dioxane)2.5] and anhydrous tetrahydro furan
It mutters to be added in reaction vessel and be heated to reflux 12~36 hours, after reaction, be cooled to room temperature, filter, with a small amount of anhydrous tetrahydro
Furans washs residue, obtains oil product after filtrate is drained, is extracted with anhydrous ether, and anhydrous n-hexane washing obtains yellowish
The intermediate product (phen) of color solid powder2C5PONa；
S2. in an inert atmosphere, reaction vessel is added in intermediate product and diphenylphosphine chlorine, dry toluene step S1 obtained
In, it is stirred at room temperature 2~6 hours, filters, obtain filtrate, ligand (phen) is obtained after filtrate is drained2C5P-O-P(phen)2；
S3. in an inert atmosphere, that ligand that step S2 is obtained is reacted 1~3 with cuprous salt CuX in anhydrous tetrahydro furan is small
When, filtering obtains solid, then washs solid with anhydrous n-hexane to get copper (I) phosphine benzene heterocycle complex is arrived；Wherein, X is halogen
Race's element.
4. copper (I) phosphine benzene heterocycle complex as claimed in claim 1 or 2 as or preparation temperature sensor in terms of application.
5. application according to claim 4, which is characterized in that the temperature sensor is fluorescence temperature sensor.
6. application according to claim 5, which is characterized in that the fluorescence temperature sensor is that metal complex insertion is high
A kind of temperature sensor of polymers film.
7. a kind of fluorescence temperature sensor, which is characterized in that be to be embedded in copper described in claim 1 (I) phosphine benzene heterocycle complex
The fluorescence temperature sensor film being prepared into high polymer.
8. fluorescence temperature sensor according to claim 7, which is characterized in that be by copper described in claim 1 (I) phosphine benzene
Heterocycle complex and high polymer are dissolved in n,N-Dimethylformamide, stir 6~10 hours, spin coating in an inert atmosphere, heating 3
~6 hours, the coordination compound film being prepared.
9. fluorescence temperature sensor according to claim 8, which is characterized in that copper (I) the phosphine benzene heterocycle complex with
The mass ratio of high polymer is 1:100~150.
10. fluorescence temperature sensor according to claim 8, which is characterized in that the high polymer is polyacrylonitrile.
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| CN103748100A (en) * | 2011-06-29 | 2014-04-23 | 辛诺拉有限公司 | Copper(I) complexes, in particular for optoelectronic components |
| CN104844629A (en) * | 2015-04-14 | 2015-08-19 | 苏州大学 | Monomer copper (I) complex material used for blue or/and green light emission |
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| CN103748191A (en) * | 2011-08-02 | 2014-04-23 | 辛诺拉有限公司 | Singlet harvesting with dual-core copper (I) complexes for optoelectronic devices |
| CN104844629A (en) * | 2015-04-14 | 2015-08-19 | 苏州大学 | Monomer copper (I) complex material used for blue or/and green light emission |
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| The cover image shows the synthesis of dinuclear copper(I) halide complexes from a new diphenylphosphinite phosphinine as chelating ligand and simple CuI halides;H. Grützmacher et al.;《Eur. J. Inorg. Chem.》;20161231;1-2，4-10 * |
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