CN107793438A - 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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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 49
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 32
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 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
- 229910004856 P—O—P Inorganic materials 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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 3
- 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 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 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
- 238000005406 washing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims 1
- 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 12
- 238000002189 fluorescence spectrum Methods 0.000 description 15
- 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
- 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
- 238000011161 development Methods 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 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
- -1 small molecule metal complex Chemical class 0.000 description 2
- 241000894007 species Species 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004699 copper complex Chemical class 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
- RRMIKQFUEXQAQP-UHFFFAOYSA-N copper;phosphane Chemical compound P.[Cu] RRMIKQFUEXQAQP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 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
- 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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- 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
- 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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- 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
- G01N21/62—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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- 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
The invention discloses a kind of copper（I）Phosphine benzene heterocycle complex and its preparation method and application.The copper（I）The structural formula of 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 life-span at room temperature is 100 microseconds, and the 77K lower life-spans are up to 2 milliseconds or so, and in the range of 77K~297K, the complex life-span has the dependence of height to temperature；Its life-span of sensor made of the complex has the linear dependence of height to temperature, and has excellent sensitivity and stability, and temperature-responsive scope 77K~337K with non-constant width；Present invention firstly discloses the copper with temperature directly perceived Yu life-span linear relationship（I）Metal complex fluorescent temperature sensor, have cost low, prepare the advantages that simple, possess great application prospect.
Description
Technical field
The invention belongs to material chemistry technical field, in particular it relates to a kind of copper（I）Phosphine benzene heterocycle complex and its preparation
Methods and applications.
Background technology
In various fields, temperature is all a crucial characteristic parameter.Temperature sensor, as what is grown up earliest
The abundant device of species, has in fields such as meteorology, aeronautics, scientific research, industry and is widely applied very much.And metal combination
Thing fluorescence temperature sensor has obtained extensive research and development with its distinctive property.They usually have the life-span of Microsecond grade,
Absorb in visible range, launch fluorescence or phosphorescence, and there is very big Stokes shift.And these metal complexs point
Sub- probe usually has certain susceptibility to oxygen, is applied to fluorescence temperature so being typically embedded in high polymer and membrane material being made
In terms of probe.At present, it is rubidium mostly to study more fluorescence temperature complexs（III）, iridium（III）, platinum（II）Deng noble metal
And europium（III）, terbium（III）, wait rare earth metal（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 that application is probably 70 from the K of room temperature 297 to the K of high temperature 350 or so
K or so, it is less 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 be 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 more high sensitivity, temperature range are wide
And can be used for the sensor of more low temperature has certain practical significance.
In addition, at present, comparatively price is higher for noble metal and rare earth metal used in existing sensor, causes fluorescence temperature
The cost for spending sensor is higher.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., which is reported, a kind of has the big steric hindrance of large-substituent containing phosphine benzene heterocycle
Cu4Br4Cluster complex, intensity and life-span gradually increase with the reduction of temperature, and this work is that first case is reported at room temperature still
Show the complex of phosphorescence.At present, on such copper containing phosphine benzene heterocycle（I）Complex report is also very rare
's（P. Roesch, J. Nitsch, M. Lutz, J. Wiecko, A. Steffen, C. Müller,Inorganic Chemistry 2014, 53, 9855-9859）.Life-span of the complex under room temperature and 77K is respectively 171 microseconds and 1516
Microsecond, not only there is the life-span higher than other complexs at room temperature, and lifetime change is very big in the temperature range,
Introducing big steric group makes the complex have the long-life.Therefore the phosphorescence copper varied with temperature based on intensity and life-span（I）Match somebody with somebody
Compound and manufactured temperature sensor are materials a kind of very novel and with development potentiality.Recently, the present inventor team
Report a kind of copper with phosphine benzene heterocycle biphosphine ligand（I）Complex, such complex equally have the life-span of Microsecond grade（X.
Chen, Z. Li, F. Yanan, H. Grützmacher, 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 in the range of room temperature and 77K
It is obvious that so there is certain limitation in terms of as fluorescence temperature sensor.
The content of the invention
The technical problems to be solved by the invention are to overcome fluorescence temperature sensor sensitivity in the prior art low, temperature model
Enclose narrow, the defects of fluorescence intensity and life-span can not vary with temperature and deficiency, there is provided a kind of phosphine benzene with excellent luminance performance
Double phosphine copper of heterocycle（I）Complex, under room temperature and low temperature, its life-span is respectively 100 microseconds and 2 milliseconds or so, can be launched
Go out the phosphorescence of crocus；And its luminous intensity and life-span can raise with the reduction of temperature, have height temperature according to
Lai Xing, fluorescence probe can be used as to be applied to prepare fluorescence temperature sensor, the hair of prepared fluorescence temperature sensor
Good linear relationship is presented with temperature in luminous intensity and life-span, and has high sensitivity, the features such as the wide range of linearity.
It is an object of the invention to provide a kind of copper（I）Phosphine benzene heterocycle complex.
It is a further object of the present invention to provide above-mentioned copper（I）The preparation method of phosphine benzene heterocycle complex and its in fluorescence temperature
Application in terms of sensor.
Another object of the present invention, which is to provide, utilizes above-mentioned copper（I）Phosphine benzene heterocycle complex prepares fluorescence temperature sensor
Method.
The above-mentioned purpose of the present 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], its structural formula such as Formulas I
It is shown：
；
Wherein, X is halogen.
The present invention increases steric hindrance, obtains a kind of intensity and life-span with temperature by adding big substituent on phosphine benzene heterocycle
Spend the complex of change.The copper of the complex（I）Cluster center is two halogen atom bridgings, two copper atoms, forms a double-core
Cu2X2Quadrangular ring-shaped structure, two copper atoms connect two phosphorus atoms of a part respectively.
Preferably, the halogen is Cl, Br or I, i.e. gained copper（I）Phosphine benzene heterocycle complex is respectively copper（I）Chlorine
Phosphine benzene heterocycle double phosphine composition, copper（I）The double phosphine compositions of bromine phosphine benzene heterocycle and copper（I）The double phosphine compositions of iodine phosphine benzene heterocycle.
Above-mentioned copper（I）The preparation method of phosphine benzene heterocycle complex, comprises the following steps：
S1. in an inert atmosphere, by 4,6- diphenyl -2- pyranone, [Na (OCP) (dioxane)2.5] and anhydrous tetrahydrochysene furan
Mutter to add in reaction vessel and be heated to reflux 12~36 hours（It is preferred that 24 hours）.Cooling, filtering, successively with anhydrous tetrahydro furan,
Absolute ether extracts, and anhydrous n-hexane washing, obtains intermediate product (phen)2C5PONa；
S2. in an inert atmosphere, intermediate product step S1 obtained and diphenylphosphine chlorine, dry toluene add reaction vessel
In, it is stirred at room temperature 2~6 hours（It is preferred that 4 hours）, filtering, part (phen) is obtained after filtrate is drained2C5P-O-P(phen)2；
S3. in an inert atmosphere, part step S2 obtained reacts 1~3 hour with cuprous salt CuX in anhydrous tetrahydro furan
（It is preferred that 2 hours）, filtering, solid is obtained, then wash solid with anhydrous n-hexane, that is, obtain complex [(phen)2C5P-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
For：1~1.2：1.
Preferably, intermediate product (phen) described in step S22C5PONa and diphenylphosphine chlorine mole ratio is：1~1.2：
1。
Preferably, part (phen) described in step S32C5P-O-P(phen)2Mole ratio with cuprous salt CuX is：1~
1.2：1.
The above-mentioned copper of the present invention（I）Phosphine benzene heterocycle complex has excellent luminescent properties, under room temperature and low temperature, its longevity
Life is respectively 100 microseconds and 2 milliseconds or so, can launch the phosphorescence of crocus；Its luminous intensity and life-span can be with temperature
The reduction of degree and raise, have 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 domain.The application is based primarily upon fluorescence intensity and life-span 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 by copper（I）Phosphine benzene heterocycle complex passes as fluorescence probe for fluorescence temperature
Sensor.
Present invention also offers a kind of fluorescence temperature sensor, is by above-mentioned copper（I）Phosphine benzene heterocycle complex [(phen)2C5P-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] and height gather
Thing is dissolved in DMF, stirs 6~10 hours（It is preferred that 8 hours）, spin coating in an inert atmosphere, it is small to heat 3~6
When（It is preferred that 4.5 hours）, you can obtain coordination compound film [(phen)2C5P-O-P(phen)2]2[Cu2Cl2]@PAN。
Preferably, the complex [(phen)2C5P-O-P(phen)2]2[Cu2X2] with the mass ratio of high polymer it 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 summary, copper of the invention（I）Phosphine benzene heterocycle complex is in room
Temperature is lower and 77K can show good phosphorescence performance.Life-span at room temperature is 100 microseconds, and the 77K lower life-spans are up to 2
Millisecond or so.In the range of 77K~297K, all complex life-spans have the dependence of height to temperature, and with higher
Sensitivity, therefore can be used for preparing fluorescence temperature sensor.Such complex is embedded in polymer polyacrylonitrile, obtained
A kind of fluorescence temperature sensor film.Its life-span of sensors with auxiliary electrode has the linear dependence of height to temperature, and with excellent
Sensitivity, it is often more important that, it has temperature-responsive scope 77K~337K of non-constant width, and the usable range is higher than report at present
Other micromolecular metal combination species temperature sensors.With regard to it is currently understood that for the research work arrived, this is first kind report
The copper with temperature directly perceived and life-span linear relationship in road（I）Metal complex fluorescent temperature sensor.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 present invention has the advantages that：
（1）Copper of the present invention（I）Phosphine benzene heterocycle complex has excellent luminosity, under room temperature and low temperature, its life-span
Respectively 100 microseconds and 2 milliseconds or so, can launch the phosphorescence of crocus, its luminous intensity and life-span can be with temperature
Reduction and raise, have height temperature dependency, fluorescence temperature sensor side can be applied to as fluorescence probe
Face, it is the good material for preparing fluorescence temperature sensor.
（2）The fluorescence temperature sensor that the present invention is prepared reaches 1.5 milliseconds or so in the life-span of room temperature, and transmitting is orange
The phosphorescence of color, with the reduction of temperature, luminous intensity and life-span and temperature are presented good linear relationship, temperature use range from
77K to 337K is up to 260K, and has very high sensitivity.
（3）The copper of the present invention（I）Phosphine benzene heterocycle complex fluorescent temperature sensor and the sensor phase of existing same type
Than there is very big temperature use range, and there is very high sensitivity.
（4）Copper of the present invention（I）Part used in complex, it is the biphosphine ligand of the very novel heterocycle of benzene containing phosphine, and it is first
It is secondary to obtain a kind of copper with temperature directly perceived with life-span linear relationship（I）Metal complex fluorescent temperature sensor.
（5）Copper of the present invention（I）Metal complex fluorescent temperature sensor is low compared with other temperature sensor costs, prepares
Simply.
Brief description of the drawings
Fig. 1 is complex [(phen)2C5P-O-P(phen)2]2[Cu2X2] route of synthesis.
Fig. 2 is the X-Ray crystal structures 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 part (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 spectras.
Fig. 8 is fluorescence temperature sensor film [(phen)2C5P-O-P(phen)2]2[Cu2Br2]@PAN fluorescence spectras.
Fig. 9 is fluorescence temperature sensor film [(phen)2C5P-O-P(phen)2]2[Cu2I2]@PAN fluorescence spectras.
Embodiment
The present invention is made with reference to Figure of description and specific embodiment and further being elaborated, the embodiment
It is served only for explaining the present invention, is not intended to limit the scope of the present invention.Test method used in following embodiments 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 bronze medal of embodiment 1（I）The preparation of the double phosphine compositions of chlorine phosphine benzene heterocycle
1st, part is prepared
（1）Under nitrogen atmosphere, will（2.0g, 8.0mmol）4,6- diphenyl -2- pyranone,（2.43 g, 8.0 mmol）[Na
(OCP)·(dioxane)2.5], and 50mL anhydrous tetrahydro furans add reaction bulb in 90 DEG C be heated to reflux 24 hours.Reaction terminates
Afterwards, cool down, filtering, successively with anhydrous tetrahydro furan, absolute ether extraction, anhydrous n-hexane washing solid, in obtaining accordingly
Between 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, by step（1）Obtained intermediate product（400 mg, 1.40 mmol）(phen)2C5PONa
With（308 mg, 1.40 mmol）Diphenylphosphine chlorine, 10 ml dry toluenes are added in reaction bulb, are stirred at room temperature 4 hours, are filtered,
Filtrate is obtained, is drained, you can obtains part (phen)2C5P-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)。
2nd, copper is prepared（I）The double phosphine compositions of chlorine phosphine benzene heterocycle
Under nitrogen atmosphere, by part 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, filtering, obtains solid, use is anhydrous
N-hexane washs solid, that is, obtains complex 1：[(phen)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 bronze medal of embodiment 2（I）The preparation of the double phosphine compositions of bromine phosphine benzene heterocycle
Part (phen)2C5P-O-P(phen)2Prepare it is same as Example 1, under nitrogen atmosphere, by part（18.6 mg,
0.13 mmol）(phen)2C5P-O-P(phen)2With（58.0 mg, 0.13 mmol）Cuprous bromide CuBr is in anhydrous tetrahydro furan
Middle reaction 2 hours, filtering, obtains solid, washs solid with anhydrous n-hexane, that is, obtain complex 2：[(phen)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 bronze medal of embodiment 3（I）The preparation of the double phosphine compositions of iodine phosphine benzene heterocycle
Part (phen)2C5P-O-P(phen)2Prepare it is same as Example 1, under nitrogen atmosphere, by part（13.6 mg,
0.07 mmol）(phen)2C5P-O-P(phen)2With（32.0 mg, 0.07 mmol）Cuprous iodide CuI is in anhydrous tetrahydro furan
Middle reaction 2 hours, filtering, obtains solid, washs solid with anhydrous n-hexane, that is, obtain 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).
The complex of embodiment 4 [(phen)2C5P-O-P(phen)2]2[Cu2Cl2] and [(phen)2C5P-O-P(phen)2]2
[Cu2Br2] X-Ray crystal structures measure
By the measure of crystal structure, shown in result figure 2, two, copper cluster center, two copper centers of halogen bridging of such part,
Form Cu2X2Double-core planar structure.
The part of embodiment 5 (phen)2C5P-O-P(phen)2With complex [(phen)2C5P-O-P(phen)2]2[Cu2X2]
The measure of ultra-violet absorption spectrum
By the measure of ultraviolet spectra, as a result as shown in figure 3, such complex has two ultraviolet absorption bands, match somebody with somebody for all
For compound, one of absorption band is respectively in 322 nm, 328 nm and 332 nm.Another absorption band is in 410 nm.And
For part, do not absorbed by force near 410 nm, two absorption bands are respectively 301 nm and 346 nm.This explanation exists
Electric charge transfer of the absorption band that 410 nm are nearby observed from part and copper cluster center.
The complex of embodiment 6 [(phen)2C5P-O-P(phen)2]2[Cu2Cl2] fluorescence spectrum measure
By to complex [(phen)2C5P-O-P(phen)2]2[Cu2Cl2] carry out fluorescence spectrum measure, shown in result figure 4,
The excitation wavelength of the complex is 410 nm, and launch wavelength is 692 nm.In the range of 77 K to 297 K, fluorescence intensity and longevity
Life reduces with the rise of temperature.It is respectively 144.4 and 2317.9 μ s in 77 K and 297 K life-spans.
The complex of embodiment 7 [(phen)2C5P-O-P(phen)2]2[Cu2Br2] fluorescence spectrum measure
By to complex [(phen)2C5P-O-P(phen)2]2[Cu2Br2] carry out fluorescence spectrum measure, as a result such as Fig. 5 institutes
Show, the excitation wavelength of the complex is 410 nm, and launch wavelength is 690 nm.In the range of 77 K to 297 K, fluorescence intensity and
Life-span reduces with the rise of temperature.It is respectively 266.6 and 1868.4 μ s in 77 K and 297 K life-spans.
The complex of embodiment 8 [(phen)2C5P-O-P(phen)2]2[Cu2I2] fluorescence spectrum measure
By to complex [(phen)2C5P-O-P(phen)2]2[Cu2I2] carry out fluorescence spectrum measure, as a result such as Fig. 6 institutes
Show, the excitation wavelength of the complex is 410 nm, and launch wavelength is 684 nm.In the range of 77 K to 297 K, fluorescence intensity and
Life-span reduces with the rise of temperature.It is respectively 63.8 and 388.4 μ s in 77 K and 297 K life-spans.
The cupric of embodiment 9（I）The preparation of the double phosphine composition fluorescence temperature sensors of phosphine benzene heterocycle
Copper prepared by embodiment 1~3（I）Complex [(phen)2C5P-O-P(phen)2]2[Cu2X2]（0.5 mg）Gather with height
Thing polyacrylonitrile（55mg）It is dissolved in DMF（1 mL）.Stirring 8 hours, the spin coating in nitrogen atmosphere.It is placed on
Heated 4.5 hours in thermal station, you can obtain coordination compound film [(phen)2C5P-O-P(phen)2]2[Cu2X2]@PAN。
The fluorescence temperature sensor of embodiment 10 [(phen)2C5P-O-P(phen)2]2[Cu2Cl2]@PAN fluorescence spectrums 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 is 590 nm.
In the range of 77 K to 337 K, fluorescence intensity and life-span reduce with the rise of temperature, and variation with temperature is presented simply
Linear relationship, its life-span sensitivity reaches 6.99 μ s/K.
The fluorescence temperature sensor of embodiment 11 [(phen)2C5P-O-P(phen)2]2[Cu2Br2]@PAN fluorescence spectrums 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 is 600 nm.
In the range of 77 K to 337 K, fluorescence intensity and life-span reduce with the rise of temperature, and variation with temperature is presented simply
Linear relationship, its life-span sensitivity reaches 4.46 μ s/K.
The fluorescence temperature sensor of embodiment 12 [(phen)2C5P-O-P(phen)2]2[Cu2I2]@PAN fluorescence spectrums 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 is 600 nm.
In the range of 77 K to 337 K, fluorescence intensity and life-span reduce with the rise of temperature, and variation with temperature is presented simply
Linear relationship, its life-span sensitivity reaches 3.71 μ s/K.
Claims (10)
- A kind of 1. copper（I）Phosphine benzene heterocycle complex, it is characterised in that its structural formula is shown in formula I：；Wherein, X is halogen.
- 2. copper according to claim 1（I）Phosphine benzene heterocycle complex, it is characterised in that the halogen is Cl, Br or I。
- 3. the copper described in claim 1 or 2（I）The preparation method of phosphine benzene heterocycle complex, it is characterised in that including following step Suddenly：S1. in an inert atmosphere, by 4,6- diphenyl -2- pyranone, [Na (OCP) (dioxane)2.5] and anhydrous tetrahydrochysene furan Mutter to add in reaction vessel and be heated to reflux 12~36 hours, after reaction terminates, be cooled to room temperature, filter, with a small amount of anhydrous tetrahydrochysene Furans washs residue, obtains oil product after filtrate is drained, is extracted with absolute ether, anhydrous n-hexane washing, obtains yellowish The intermediate product (phen) of color solid powder2C5PONa；S2. in an inert atmosphere, intermediate product step S1 obtained adds reaction vessel with diphenylphosphine chlorine, dry toluene In, it is stirred at room temperature 2~6 hours, filters, obtain filtrate, part (phen) is obtained after filtrate is drained2C5P-O-P(phen)2；S3. in an inert atmosphere, that the part that step S2 is obtained is reacted into 1~3 in anhydrous tetrahydro furan with cuprous salt CuX is small When, filtering, solid is obtained, then wash solid with anhydrous n-hexane, that is, obtain copper（I）Phosphine benzene heterocycle complex；Wherein, X is halogen Race's element.
- 4. the copper of claim 1 or 2（I）Phosphine benzene heterocycle complex as or preparation temperature sensor in terms of application.
- 5. application according to claim 4, it is characterised in that the temperature sensor is fluorescence temperature sensor.
- 6. application according to claim 5, it is characterised 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, it is characterised in that be by copper described in claim 1（I）Phosphine benzene heterocycle complex is embedded in The fluorescence temperature sensor film being prepared into high polymer.
- 8. fluorescence temperature sensor according to claim 7, it is characterised in that be by copper described in claim 1（I）Phosphine benzene Heterocycle complex and high polymer are dissolved in DMF, 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, it is characterised in that the copper（I）Phosphine benzene heterocycle complex with The mass ratio of high polymer is 1:100~150.
- 10. fluorescence temperature sensor according to claim 8, it is characterised in that the high polymer is polyacrylonitrile.
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| CN108456217A (en) * | 2018-03-23 | 2018-08-28 | 南京晓庄学院 | A kind of fluorescence temperature measuring appliance hybrid material and preparation method and application |
| CN109776614A (en) * | 2019-03-25 | 2019-05-21 | 中国计量大学 | A kind of cuprous complex fluorescent sensing material of pair of 4- picoline steam selective response |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108456217A (en) * | 2018-03-23 | 2018-08-28 | 南京晓庄学院 | A kind of fluorescence temperature measuring appliance hybrid material and preparation method and application |
| CN108456217B (en) * | 2018-03-23 | 2019-01-25 | 南京晓庄学院 | A kind of fluorescence temperature measuring appliance hybrid material and preparation method and application |
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| CN109776614A (en) * | 2019-03-25 | 2019-05-21 | 中国计量大学 | A kind of cuprous complex fluorescent sensing material of pair of 4- picoline steam selective response |
| CN109776614B (en) * | 2019-03-25 | 2021-03-19 | 中国计量大学 | Cuprous complex fluorescent sensing material selectively responding to 4-methylpyridine steam |
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