CN109970769B - Diquinolinylphosphine cuprous (I) halide complex, preparation method and application thereof, OLED assembly method and photocatalyst - Google Patents
Diquinolinylphosphine cuprous (I) halide complex, preparation method and application thereof, OLED assembly method and photocatalyst Download PDFInfo
- Publication number
- CN109970769B CN109970769B CN201910184550.6A CN201910184550A CN109970769B CN 109970769 B CN109970769 B CN 109970769B CN 201910184550 A CN201910184550 A CN 201910184550A CN 109970769 B CN109970769 B CN 109970769B
- Authority
- CN
- China
- Prior art keywords
- complex
- complexes
- copper
- cuprous
- halide complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000004820 halides Chemical class 0.000 title claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 Diquinolinylphosphine Chemical compound 0.000 title claims description 9
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052740 iodine Chemical group 0.000 claims description 4
- 239000011630 iodine Chemical group 0.000 claims description 4
- 238000001771 vacuum deposition Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 abstract description 14
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 abstract description 4
- 150000001879 copper Chemical class 0.000 abstract description 3
- AYQQDOXLJACYIW-UHFFFAOYSA-N phenyl-di(quinolin-8-yl)phosphane Chemical group C1=CC=CC=C1P(C=1C2=NC=CC=C2C=CC=1)C1=CC=CC2=CC=CN=C12 AYQQDOXLJACYIW-UHFFFAOYSA-N 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 26
- 229960000907 methylthioninium chloride Drugs 0.000 description 26
- 239000003446 ligand Substances 0.000 description 13
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910017888 Cu—P Inorganic materials 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGDAGYXJBDILKZ-UHFFFAOYSA-N [2-methyl-1,1-dioxo-3-(pyridin-2-ylcarbamoyl)-1$l^{6},2-benzothiazin-4-yl] 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 LGDAGYXJBDILKZ-UHFFFAOYSA-N 0.000 description 1
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- JWTSNWDILVPNHA-UHFFFAOYSA-N phosphane;quinoline Chemical compound P.N1=CC=CC2=CC=CC=C21 JWTSNWDILVPNHA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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 System
- C07F1/08—Copper compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the technical field of copper complexes, and particularly relates to a biquinoline phenylphosphine cuprous (I) halide complex, a preparation method and application thereof, an OLED assembly method and a photocatalyst. The present invention provides tetracoordinated mononuclear dinoquinoline phenylphosphine cuprous halide complexes [ cux (ppdq)) ] (ppdq ═ 8- [ phenyl (8-quinolinyl) phosphino ] quinoline, X ═ I (1), Br (2), and Cl (3)). The provided complex emits blue-green to red-violet light at room temperature, and the maximum emission wavelength is 503-800 nm. The three complexes have better thermal stability and good catalytic performance.
Description
Technical Field
The invention belongs to the technical field of copper complexes, and particularly relates to a biquinoline phenylphosphine cuprous (I) halide complex, a preparation method and application thereof, an OLED assembly method and a photocatalyst.
Background
The use of transition metal complexes in Organic Light Emitting Diodes (OLEDs) has attracted considerable attention over the last decades. Particularly, heavy transition metals such as iridium (III) and pt (ii), etc., can trap triplet emission due to excellent spin-orbit coupling, theoretically can obtain 100% internal quantum efficiency, and are considered to greatly improve the external quantum efficiency of the electroluminescent device. However, iridium and platinum are expensive and low in natural abundance, which hinders the popularization and application of OLEDs to some extent. The selection of a metal with high natural abundance and low price, such as a copper complex, as a substitute has become a current research hotspot.
Copper (I) as typical d10Metals that can be used to construct materials with low MLCT excited states and small singlet-triplet energy gaps (Δ E)ST) And can efficiently trap triplet excitons that generate Thermally Activated Delayed Fluorescence (TADF) emission.
The development of catalytic technology in the removal of organic pollutants from wastewater has received much attention. Some results indicate that the copper (I) complex is an effective catalyst for degradation of organic dyes. For example, Cui reports a series of cu (i) complexes that exhibit excellent photocatalytic degradation activity of Methylene Blue (MB) under uv light irradiation. The preparation of neutral copper (I) complexes using different halogen and phosphine nitrogen ligands remains a challenge. TADF in copper complexes remains difficult to predict because it is a property of the excited state.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a biquinoline phenylphosphine cuprous (I) halide complex, a preparation method and application thereof, an OLED assembly method and a photocatalyst.
The technical scheme provided by the invention is as follows:
the copper (I) biquinoline phenylphosphine halide complex is characterized by having the following structural general formula:
wherein, X is chlorine, bromine or iodine.
The four-coordination mononuclear biquinoline phenylphosphine cuprous halide complex provided by the technical scheme has good thermal stability and catalytic performance, and can be used as an OLED luminescent material. The general chemical formula of the provided complexes is cux (ppdq), ppdq ═ 8- [ phenyl (8-quinolyl) phosphino ] quinoline, X ═ I (complex 1), Br (complex 2) and Cl (complex 3).
Preferably, X is bromine.
The complex provided by the technical scheme has good thermal stability and catalytic performance, has a TADF (TADF) effect, and can be used as an OLED (organic light emitting diode) luminescent material. The invention also provides a preparation method of the copper (I) biquinoline phenylphosphine halide complex, which has the following reaction formula:
wherein, X is chlorine, bromine or iodine.
The biquinoline phenylphosphine cuprous halide (I) complex can be conveniently prepared by the method. The prepared di-quinoline phenylphosphine cuprous (I) halide complex has good thermal stability and catalytic performance, and can be used as an OLED luminescent material.
Preferably, X is bromine.
The complex prepared by the technical scheme has good thermal stability and catalytic performance, has TADF effect, and can be used as an OLED luminescent material.
The invention also provides application of the biquinoline phenylphosphine cuprous (I) halide complex as an organic light-emitting diode material.
The biquinoline phenylphosphine cuprous halide (I) complex can emit blue-green to red-violet light at room temperature, the maximum emission wavelength is 503-800nm, and luminescence mainly comes from MLCT, XLCT and charge transition in a ligand and can be used as a luminescent material.
The invention also provides an assembly method of the OLED, which comprises the following steps: the biquinoline phenylphosphine cuprous (I) halide complex provided by the invention is evaporated by a vacuum evaporation method.
The biquinoline phenylphosphine cuprous (I) halide complex provided by the invention can be used as an OLED luminescent material, has high thermal decomposition temperature and good thermal stability, and can be used for assembling an OLED by a vacuum evaporation method.
The invention also provides application of the biquinoline phenylphosphine cuprous (I) halide complex as a photocatalyst.
The complex provided by the invention is a good photocatalyst for decomposing dye under natural light, and the highest catalytic efficiency reaches 90%.
The invention also provides a photocatalyst which comprises the biquinoline phenylphosphine cuprous halide (I) complex.
The complex provided by the invention is a good photocatalyst for decomposing dye under natural light, and can be used as a photocatalyst or a component of a composite photocatalyst.
Drawings
FIG. 1 is an ORTEP diagram of complex 1 in practice.
FIG. 2 is an ORTEP diagram of Complex 2 in practice.
FIG. 3 is an ORTEP diagram of complex 3 in practice.
FIG. 4 shows ppdq and complexes 1-3 in CH at room temperature2Cl2Absorption spectrum of (1).
FIG. 5 is the emission spectrum of complexes 1-3 in the solid state at 295K.
FIG. 6 is the emission spectrum of complex 1-3 in the solid state at 77K.
FIG. 7 is a CIE diagram of complexes 1-3.
FIG. 8 is a TGA profile of complexes 1-3.
FIG. 9 shows the degradation of methylene blue catalyzed by complexes 1-3.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Reagent: all reagents were commercially available and analytically pure. Tetrahydrofuran was used before water was re-evaporated over sodium wire under nitrogen atmosphere and benzophenone was used as indicator. Ligand ppdq was synthesized according to literature methods (x.l.wang, j.luan, f.f.sui, h.y.lin, g.c.liu, c.xu, crystal.growth des.2013,13,3561).
The instrument comprises the following steps: the infrared spectrum was obtained by means of a Fourier transform infrared spectrometer (KBr pellet) of the BX FI-IR type from Perkin Elmet of USA,1h and31p NMR spectra were obtained using a Varian 500MHz NMR spectrometer using deuterium-loaded reagent lock fields and references, chemical shifts were measured in ppm and H spectra were measured in SiMe4As a standard, the phosphorus spectrum is 85% H3PO4Is a standard. The high resolution mass spectrum adopts a Bruker Autoflex MALDI-TOF mass spectrometer, and the elemental analysis adopts a Vario Micro Cube elemental analyzer. The single crystal structure of the complex 1-3 adopts a Bruker APEX DUO diffractometer. The ultraviolet visible spectrum adopts a Unicam He lambda ios alpha spectrometer, and the photoluminescence spectrum adopts an FLS920 steady-state and time-resolved fluorescence spectrometer. The solid state quantum efficiency is measured by using a Hamamatsu system and an integrating sphere. Thermogravimetric analysis A Perkin-Elmer Diamond TG/DTA thermal analyzer was used.
Synthesis of Complex 1
Cuprous iodide (0.105g,0.55mmol) was added to 30mL CH in which ppdq (0.200g,0.55mmol) was dissolved2Cl2Stirring the mixture at room temperature in the dark to form a red suspension, filtering the reaction mixture, removing the solvent under reduced pressure to obtain a red powder, and adding CH2Cl2Recrystallization gave 0.257g, 84.3% red crystals.1H NMR(500MHz,DMSO-d6)δ:9.24(d,J＝4Hz,2H),8.63(d,J＝10Hz,2H),8.38(t,J＝5Hz,2H),8.21(d,J＝10Hz,2H),7.80(t,J＝5Hz,4H),7.52(d,J＝5Hz,5H).31P NMR(200MHz,DMSO-d6),δ＝-41.05(s).Anal.Calcd for C24H17CuIN2P:C,51.95；H,3.09；N,5.05.Found:C,51.98；H,3.11；N,5.07.MS(MALDI-TOF):m/z calcd for[C24H17CuIN2P]+553.9470 Found 554.1203, the structure of which is shown in FIG. 1.
Synthesis of Complex 2
Cuprous bromide (0.079g,0.55mmol) was added to 30mL CH in which ppdq (0.200g,0.55mmol) was dissolved2Cl2In the solution, the mixture is stirred at room temperature in the dark to form red suspensionFiltering the reaction mixture, removing the solvent under reduced pressure to obtain red powder, and dissolving with CH2Cl2Recrystallization gave 0.238g, 85.3% red crystals.1H NMR(500MHz,DMSO-d6)δ:9.18(d,J＝3Hz,2H),8.61(d,J＝10Hz,2H),8.36(t,J＝8Hz,2H),8.20(d,J＝5Hz,2H),7.79(t,J＝8Hz,4H),7.52-7.45(m,5H).31P NMR(200MHz,DMSO-d6),δ＝-42.61(s).Anal.Calcd for C24H17CuBrN2P:C,56.76；H,3.37；N,5.52.Found:C,56.78；H,3.38；N,5.53.MS(MALDI-TOF):m/z calcd for[C24H17CuBrN2P]+505.9609 mount: 506.1057, the structure of which is shown in FIG. 2.
Synthesis of Complex 3
Cuprous chloride (0.054g,0.55mmol) was added to 30mL CH in which ppdq (0.200g,0.55mmol) was dissolved2Cl2Stirring the mixture at room temperature in the dark to form a red suspension, filtering the reaction mixture, removing the solvent under reduced pressure to obtain a red powder, and adding CH2Cl2Recrystallization gave 0.213g, 83.9% red crystals.1H NMR(500MHz,DMSO-d6)δ:9.39(s,2H),8.25(d,J＝10Hz,4H),7.92(d,J＝10Hz,2H),7.60(d,J＝25Hz,4H),7.50-7.34(m,5H).31PNMR(200MHz,DMSO-d6),δ＝-38.77(s).Anal.Calcd for C24H17CuBrN2P:C,62.21；H,3.70；N,6.05.Found:C,62.24；H,3.71；N,6.07.MS(MALDI-TOF):m/z calcd for[C24H17CuClN2P]+462.0114.Found:462.0186. the structure is shown in FIG. 3.
Catalytic experiment
The catalytic activity of complexes 1-3 was tested using Methylene Blue (MB) as an organic contaminant model. The catalytic activity of complexes 1-3 was tested. 50mL of methylene blue aqueous solution (10mg/L) and 15mg of each of complexes 1 to 3 were added to 3 100mL round-bottom flasks at room temperature, and 2mL of 30% H was added to each flask2O2The solution pH was adjusted to 3 with concentrated sulfuric acid. Under the experimental conditions, complexes 1-3 were not soluble in the reaction mixture. At regular intervals, 4.0mL of the reaction solution was removed and filtered to remove residual catalystAn oxidizing agent. The change in the concentration of Methylene Blue (MB) was monitored by measuring the uv-visible spectrum of the solution using uv spectrophotometer and detecting the absorbance at 662 nm. As a control experiment under the same conditions, the process was repeated without catalyst. The degradation efficiency of Methylene Blue (MB) was evaluated according to the following formula:
wherein C is0(mg·L-1) Is the initial concentration of methylene blue, Ct(mg·L-1) Is the concentration of methylene blue at the reaction time t (h).
Characterization of
1 equivalent of ppdq ligand was mixed with 1 equivalent of CuX (X ═ I for 1, Br for 2, Cl for 3) in dichloromethane, and after isolation and purification, complex 1-3 was obtained with a yield of 83.9-85.3%. All cu (i) complexes are air stable and of high purity, soluble in common organic solvents such as dichloromethane, chloroform, acetonitrile and DMSO. The structures of the compounds are characterized by nuclear magnetism, mass spectrum, single crystal X-ray diffraction and the like.
The structures of complexes 1-3 are shown in FIG. 1, FIG. 2 and FIG. 3, respectively. The crystal data and partial bond length and bond angle data are shown in tables 1 and 2. The mononuclear copper (I) center is connected to one P, two N and one halogen atom, exhibiting a highly distorted tetrahedral coordination. The bond angle of N-Cu-P is 85.06-86.79 DEG, which is much lower than the bond angle of a regular tetrahedron, because the ligand ppdq has a small bite angle. As shown in Table 2, the Cu-X bond length of complexes 1-3 increases with the increase of the Van der Waals radius of the halogen. 1. The dihedral angles between the P-Cu-X plane and the 2 quinoline rings in 2 and 3 were 63.21/53.65, respectively; 58.29 deg./50.67 deg. and 54.09 deg./53.65 deg.. 1 and 3, with the closest distances of I-to-H and Cl-to-H, respectively
And
in the solid state, the water-soluble polymer,1-3, an intermolecular C-H … pi interaction exists between the quinoline ring and the benzene ring, wherein the closest C-to-H distances are respectively
And
all these intermolecular forces cause the complex to form a 1D chain structure along the a, b and c axes, respectively.
TABLE 1 Crystal data for complexes 1-3
TABLE 2 partial bond lengths and bond angles of complexes 1 to 3
Photophysical properties
FIG. 4 shows ligands ppdq and complexes 1-3 at room temperature in CH2Cl2Absorption spectrum of (1). The concentration of the ligand and the complex is 5X 10-5M, absorption spectrum of ppdq at 335nm (ε 4.50 × 103M-1cm-1) Has a wide strong band, which is the characteristic absorption ultraviolet peak of the quinoline phosphine and phenyl phosphine compounds. This absorption band can be attributed to the charge transitions of pi → pi and n → pi in the ligand ppdq. The absorption spectrum of the complex 1-3 is 303-305nm [. epsilon. - (1.52-2.21) × 10-3M-1cm-1]Has a strong absorption band at 385-572nm and a weaker absorption tail band at 385-572nm, which is attributable to the fact that the transition is caused by MLCT, XLCT and ligand。
FIG. 5 and FIG. 6 show the excitation wavelength λexc345nm, the solid state emission spectra of the complexes 1-3 at 295K and 77K, and Table 3 shows the maximum emission wavelength, the lifetimes of 295K and 77K, the quantum efficiency, and the calculated data of the time-density functional theory (TDDFT) obtained by X-ray crystal structure analysis. The complex emits blue-green to red-violet light from 1-3 at room temperature, the maximum emission wavelength is 503-800nm, and the quantum yield at room temperature is less than 0.01. The luminescence intensity of complexes 1 and 3 is significantly weaker than 2. The emission spectrum of the complex 1-3 is wide, and the emission excited state has charge transfer characteristics. Based on TDDFT calculations, the emission excited states of 1-3 are attributed to MLCT and XLCT and charge transitions within the ligand. 1-3 has an emission maximum wavelength order of 1>2>3, opposite order of field strengths of the halogen ligands (I)<Br<Cl)。
Based on the fluorescence spectrum of the complex 1-3 at 295K, the chromaticity coordinate values are (0.3336,0.1868), (0.653,0.3409), (0.2345,0.3512), respectively, as shown in FIG. 7. At 77K, complexes 1-3 emitted at 800,576 and 490nm, the emission bands of complexes 2 and 3 were blue-shifted (13-87nm) compared to the maximum emission wavelength at room temperature, probably because the energy release from the excited state due to the structural change caused by vibration and rotation was suppressed at low temperatures. We have found that the lifetime of complex 2 at 295K (1.8 μ s) is 1 order of magnitude shorter than the lifetime of 77K (49.5 μ s), providing evidence of TADF for complex 2. In comparison to complex 2, at 77K, complexes 1 and 3 emitted much less intense light than complex 2 and much less intense light than 295K. The luminescence lifetime of complex 1 was 10.3ns, corresponding to fast fluorescence, not TADF. Whereas the 77 lifetime (3.0us) of complex 3 is lower than the room temperature lifetime (48.1us), in contrast to complex 2 with TADF, it is possible that T of complex 31Unstable, resulting in shortened life. S calculated by TDDFT0,S1And T1The change of bond length bond angle in this state can be seen in that the bond length bond angles of complexes 1 and 3 are greatly changed, and more energy is dissipated by vibration rotation and the like, which is also the main reason for the weak luminescence of complexes 1 and 3.
Table 3.Photophysical data of 1–3in the solid state.
aWavelength of emission peak indicates that the emission peak is shoulder peak or weak peak
bMean life τave＝∑BiTi 2/∑BiTi,TiShown in parentheses, experimental error ± 5%.
cAbsolute quantum efficiency in solid state, experimental error ± 5%.
dNanosecond
Thermal properties
The good thermal stability of the complexes is very important for the application of OLEDs, and therefore the thermal properties of complexes 1 to 3, the initial decomposition temperature (T) of complexes 1 to 3, were investigated by thermo-gravimetric analysis (TGA) in a nitrogen streamdec) As determined by thermogravimetric analysis (TGA) under a nitrogen stream, as shown in figure 8. T of Complex 1-3decAt 379 ℃ and 391 ℃, significant weight loss was exhibited between 452 ℃ and 484 ℃, approximately 57-66% weight loss, attributable to loss of ppdq ligand. The high thermal decomposition temperature indicates that the complex 1-3 has good thermal stability, and the OLED can be assembled by adopting a vacuum evaporation method.
Catalytic properties
Methylene Blue (MB) is commonly used to evaluate the catalytic activity of catalysts in wastewater purification, so we chose MB as a dye pollutant model to study the catalytic properties of complexes 1-3 in detail under natural light. MB has a characteristic absorption at approximately 662nm and is used to monitor the degradation process. Furthermore, under the same conditions as the control experiment, the degradation of MB without any addition of complex was also investigated. In the control experiment, no significant decrease in MB absorbance values was shown over the time frame of the experiment. However, when the complexes 1 to 3 were added to the MB solution, the absorption peaks of MB gradually decreased with the increase of the reaction time, indicating that the complexes 1 to 3 were catalytically active for the degradation of MB. FIG. 9 is a graph showing the change in the concentration (C) of MB with the reaction time (t). It can be seen that over time, the MB concentration is clearly apparent in the presence of complexes 1-3And decreases. At pH 3, MB decomposed approximately 81%, 83%, and 90% in complexes 1-3, respectively, over 24 hours. Without the addition of the complex, the degradation efficiency of MB was only 6.7%. This indicates H2O2The MB dye alone cannot be degraded. The results of catalytic experiments show that the complex 1-3 is a good catalyst for decomposing dyes. The experimental results show that the catalytic effect is 3>2>1。
The invention provides a series of novel neutral mononuclear four-coordination biquinoline phenylphosphine cuprous halide (I) complexes. The complex 1-3 emits blue-green to red-violet light at room temperature, and the maximum emission wavelength is 503-800 nm. Luminescence mainly originates from MLCT, XLCT and charge transition in ligand. The complex 2 has TADF effect at room temperature, and the luminescence of the complex 1 belongs to fast fluorescence. The three complexes have good thermal stability. The low luminescence quantum yield (<0.01) is mainly due to the poor rigid environment around the copper center, which leads to radiationless deactivation. The catalytic experiment result shows that under natural light, the complex 1-3 is a good catalyst for decomposing dye, and the catalytic efficiency is up to 90 percent at most.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The copper (I) biquinoline phenylphosphine halide complex is characterized by having the following structural general formula:
wherein, X is chlorine, bromine or iodine.
2. Copper (I) biquinolinylphosphine halide complex according to claim 1, characterized in that: x is bromine.
3. The preparation method of the copper (I) biquinoline phenylphosphine halide complex is characterized by comprising the following reaction formula:
wherein, X is chlorine, bromine or iodine.
4. The process for preparing copper (I) biquinolinylphosphine halides according to claim 3, characterized in that: x is bromine.
5. Use of a copper (I) bis-quinolinylphosphine halide complex according to claim 1 or 2, characterized in that: as organic light emitting diode materials.
6. A method of assembling an OLED comprising the steps of: evaporating the copper (I) biquinolinylphosphine halide complex as described in claim 1 or 2 by a vacuum evaporation method to obtain an OLED light-emitting layer.
7. Use of a copper (I) diquinolinylphosphine halide complex according to claim 1 or 2, characterized in that: as a photocatalyst.
8. A photocatalyst comprising the copper (I) biquinolinylphosphine halide complex according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910184550.6A CN109970769B (en) | 2019-03-12 | 2019-03-12 | Diquinolinylphosphine cuprous (I) halide complex, preparation method and application thereof, OLED assembly method and photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910184550.6A CN109970769B (en) | 2019-03-12 | 2019-03-12 | Diquinolinylphosphine cuprous (I) halide complex, preparation method and application thereof, OLED assembly method and photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109970769A CN109970769A (en) | 2019-07-05 |
| CN109970769B true CN109970769B (en) | 2021-09-21 |
Family
ID=67078567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910184550.6A Active CN109970769B (en) | 2019-03-12 | 2019-03-12 | Diquinolinylphosphine cuprous (I) halide complex, preparation method and application thereof, OLED assembly method and photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109970769B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002079207A2 (en) * | 2001-04-02 | 2002-10-10 | California Institute Of Technology | Tri-and bidentate amido ligands prepared by palladium0 coupling and metallation thereof to form metal-amido catalysts |
| CN101927175A (en) * | 2009-06-26 | 2010-12-29 | 中国科学院福建物质结构研究所 | Heteropolyacid material constructed by Dawson type polyacid and six-core copper complex, and preparation method and application thereof |
| WO2013120057A1 (en) * | 2012-02-10 | 2013-08-15 | The Regents Of The University Of California | First row metal-based catalysts for hydosilylation |
| CN103467313A (en) * | 2013-09-09 | 2013-12-25 | 合肥工业大学 | Chiral copper complex |
| CN104003828A (en) * | 2014-06-06 | 2014-08-27 | 天津师范大学 | Preparation method of amine and aromaticnitrile coupling reaction catalyzed by copper complex under visible light |
| CN109824722A (en) * | 2019-02-26 | 2019-05-31 | 湖北大学 | Dinitrogen list phosphine compound and its preparation method and application and cuprous halide complex and its preparation method and application |
-
2019
- 2019-03-12 CN CN201910184550.6A patent/CN109970769B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002079207A2 (en) * | 2001-04-02 | 2002-10-10 | California Institute Of Technology | Tri-and bidentate amido ligands prepared by palladium0 coupling and metallation thereof to form metal-amido catalysts |
| CN101927175A (en) * | 2009-06-26 | 2010-12-29 | 中国科学院福建物质结构研究所 | Heteropolyacid material constructed by Dawson type polyacid and six-core copper complex, and preparation method and application thereof |
| WO2013120057A1 (en) * | 2012-02-10 | 2013-08-15 | The Regents Of The University Of California | First row metal-based catalysts for hydosilylation |
| CN103467313A (en) * | 2013-09-09 | 2013-12-25 | 合肥工业大学 | Chiral copper complex |
| CN104003828A (en) * | 2014-06-06 | 2014-08-27 | 天津师范大学 | Preparation method of amine and aromaticnitrile coupling reaction catalyzed by copper complex under visible light |
| CN109824722A (en) * | 2019-02-26 | 2019-05-31 | 湖北大学 | Dinitrogen list phosphine compound and its preparation method and application and cuprous halide complex and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Direct Evidence for an SN1CB Mechanism. 4. Crystal and Molecular Structure of Chloro(bis(8-quinolinyl)amido-7V1,N2,N3)copper(II), a Metal Chelate Containing an sp2-Hybridized Deprotonated Amine;Jeffrey L. Petersen et al.;《Inorg.Chem.》;19861231;第25卷(第21期);3837-3840 * |
| Luminescent complexes of the zinc triad withN-substituted 8-amino-quinoline ligands: Synthesis and comparative study on the stability constants and related photophysical properties;Luciano Canovese et al.;《Inorganica Chimica Acta》;20090518;第362卷;3925-3933 * |
| Phenanthridine-Containing Pincer-like Amido Complexes of Nickel,Palladium, and Platinum;David E. Herbert et al.;《Inorg. Chem. 》;20170307;第56卷;3674-3685 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109970769A (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Two anthracene-based metal–organic frameworks for highly effective photodegradation and luminescent detection in water | |
| Yang et al. | A Zn-MOF constructed from electron-rich π-conjugated ligands with an interpenetrated graphene-like net as an efficient nitroaromatic sensor | |
| Qu et al. | Zn (ii)/Cd (ii)-based metal–organic frameworks: Crystal structures, Ln (iii)-functionalized luminescence and chemical sensing of dichloroaniline as a pesticide biomarker | |
| Femoni et al. | New tetrazole-based Cu (I) homo-and heteroleptic complexes with various P^ P ligands: synthesis, characterization, redox and photophysical properties | |
| Sun et al. | Metal–organic framework composites with luminescent gold (III) complexes. Strongly emissive and long-lived excited states in open air and photo-catalysis | |
| JP5818864B2 (en) | Triphenylene derivatives in novel organometallic complexes emitting in the red to green spectral region and their use in OLEDs | |
| Artem'Ev et al. | Bright green-to-yellow emitting Cu (I) complexes based on bis (2-pyridyl) phosphine oxides: synthesis, structure and effective thermally activated-delayed fluorescence | |
| He et al. | Design and synthesis of luminescence chemosensors based on alkynyl phosphine gold (I)–copper (I) aggregates | |
| Mondal et al. | Nickel (II), copper (I) and zinc (II) complexes supported by a (4-diphenylphosphino) phenanthridine ligand | |
| Wen et al. | Two luminescent Cu (I) coordination polymers based on the 1-(4-tetrazolephenyl) imidazole ligand for sensing of nitrobenzene | |
| Yang et al. | The effect of two additional Eu 3+ lumophors in two novel trinuclear europium complexes on their photoluminescent properties | |
| Sun et al. | Two novel lead (ii)-tetrazolate frameworks based on cubane [Pb 4 (OH) 4] 4+ clusters trapping long lifetime luminescence emission | |
| Jia et al. | Synthesis and characterization of a novel cyanostilbene derivative and its initiated polymers: aggregation-induced emission enhancement behaviors and light-emitting diode applications | |
| Zhang et al. | Photo-and electro-luminescence of four cuprous complexes with sterically demanding and hole transmitting diimine ligands | |
| JP2011256122A (en) | Guest-responsive light emitting material | |
| Zhu et al. | Metal–organic frameworks assembled from flexible alicyclic carboxylate and bipyridyl ligands for sensing of nitroaromatic explosives | |
| CN101717629B (en) | Optical oxygen sensing composite material and preparation method thereof | |
| Yang et al. | Syntheses, crystal structures and optical properties of six homochiral coordination networks based on phenyl acid-amino acids | |
| Verma et al. | Luminescent metal organic frameworks for sensing and gas adsorption studies | |
| Du et al. | Self-assembly of two supramolecular indium (iii) metal–organic frameworks for reversible iodine capture and large band gap change semiconductor behavior | |
| CN109824722B (en) | Bisphosphoryl monophosphine compound, preparation method and application thereof, cuprous halide complex, preparation method and application thereof | |
| Gangan et al. | Tuning of the excitation wavelength in Eu 3+-aminophenyl based polyfluorinated β-diketonate complexes: a red-emitting Eu 3+-complex encapsulated in a silica/polymer hybrid material excited by blue light | |
| Han et al. | Temperature-induced structural diversity of metal–organic frameworks and their applications in selective sensing of nitrobenzene and electrocatalyzing the oxygen evolution reaction | |
| Yan et al. | Blue Electrophosphorescence from Iridium (III) Phosphors Bearing Asymmetric Di‐N‐aryl 6‐(trifluoromethyl)‐2H‐imidazo [4, 5‐b] pyridin‐2‐ylidene Chelates | |
| CN109970769B (en) | Diquinolinylphosphine cuprous (I) halide complex, preparation method and application thereof, OLED assembly method and photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |