CN107722066A - The preparation method and its oxygen Application in Sensing of platinum complex containing triphenylamine - Google Patents
The preparation method and its oxygen Application in Sensing of platinum complex containing triphenylamine Download PDFInfo
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- CN107722066A CN107722066A CN201711131741.3A CN201711131741A CN107722066A CN 107722066 A CN107722066 A CN 107722066A CN 201711131741 A CN201711131741 A CN 201711131741A CN 107722066 A CN107722066 A CN 107722066A
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- Prior art keywords
- diketone
- platinum complex
- assistant ligand
- reaction
- triphenylamine
- 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.)
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 44
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000001301 oxygen Substances 0.000 title abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract 4
- 239000003446 ligand Substances 0.000 claims abstract description 21
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940095102 methyl benzoate Drugs 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- -1 platinum ion Chemical class 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- PAMBVPQLDDXPCQ-UHFFFAOYSA-N boric acid;n,n-diphenylaniline Chemical compound OB(O)O.C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 PAMBVPQLDDXPCQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000005594 diketone group Chemical group 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 206010001497 Agitation Diseases 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OPWOOOGFNULJAQ-UHFFFAOYSA-L azane;cyclopentanamine;2-hydroxybutanedioate;platinum(2+) Chemical compound N.[Pt+2].NC1CCCC1.[O-]C(=O)C(O)CC([O-])=O OPWOOOGFNULJAQ-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 101150050192 PIGM gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- 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
-
- 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
-
- 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
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The preparation method and its oxygen Application in Sensing of beta diketone assistant ligand platinum complex containing triphenylamine, it belongs to luminescent material technical field.The complex is synthesized by 2 phenylpyridine C^N type rings metal ligands with by parabromoacetophenone, methyl benzoate and 4 triphenylamine boric acidβDiketone assistant ligand is complexed platinum ion and formed jointly.The platinum complex that the present invention synthesizes has good oxygen sensing capabilities, and phosphorescence quenching and recovery process are reversible.Oxygen concentration can be monitored on-line with the lambda sensor of its preparation.
Description
Technical field
The present invention relates to containing triphenylamineβThe preparation method and its oxygen Application in Sensing of-diketone assistant ligand-platinum complex,
It belongs to luminescent material technical field.
Background technology
Lambda sensor is widely used (Opt. in the numerous areas such as biomedical, Food Science and environment measuring
Express 2009, 17, 22341-22350; Bulg. Chem. Commun. 2013, 45; J. Environ. Eng.
2007,133,655-658) it is significant, therefore, to develop efficient, quick, sensitive oxygen detection technique.Luminescent oxygen passes
Sense technology using oxygen molecule quenching oxygen responsive probe (Oxygen-sensitive probes, OSPs) phosphorescence (or delay it is glimmering
Light) principle realize detection to oxygen concentration.OSPs and ground state (triplet in the first triplet excited state (T1 states)）
Dynamic occurs for oxygen molecule（Diffusion control）Collision, OSPs T1 states energy pass to oxygen molecule by collision, the phosphorescence of itself
（Or delayed fluorescence）Be quenched, collision process along with singlet state molecular oxygen generation.Luminous lambda sensor has inspection due to it
Not the advantages that oxygen consumption, precision is not good during survey, the degree of accuracy is high, achievable long-range oxygen concentration detects and is easy to miniaturization, by
To the extensive concern of people.
Cycloplatin (II) complex has the advantages that lifetime of excited state is long, visible region absorption is strong, photostability is strong, is a kind of
The OSPs (J. Am. Chem. Soc. 1977,99 (11), 3547-3551) of excellent performance.Can by the modification to part
Effectively to adjust the optical physics of complex and electrochemical properties, and adjust its oxygen sensing capabilities (Dyes Pigm. 2014,
101, 85-92; J. Mater. Chem. C 2015, 3, 2166-2174)。
β- diketonate ligand is a kind of important bidentate ligand, is usually used in that coordination occurs with transiting state metal so as to improve its light
The stability and reactivity (J. Mater. Chem. 2010,20,2063-2070) of mutagens color system.β- diketonate ligand
Assistant ligand can be used as to be coordinated with platinum.Pass through changeβThe property of-diketone assistant ligand also can be to the optical physics and electrification of complex
Property is learned to make a significant impact.
The content of the invention
It is an object of the invention to provide containing triphenylamineβThe preparation method and its oxygen of-diketone assistant ligand-platinum complex pass
Sensing is used.
The technical solution adopted by the present invention is：Containing triphenylamineβ- diketone assistant ligand-platinum complex, by 2- phenylpyridines
Synthesized with parabromoacetophenone, methyl benzoate and 4- triphenylamine boric acidβ- diketone assistant ligand is complexed platinum ion shape jointly
Into its structure is as follows：
。
The specific synthesis step of the platinum complex is as follows：
(1)β- diketone assistant ligand synthesizes
Sodium hydride, tetrahydrofuran and methyl benzoate are sequentially added into two mouthfuls of flasks of round bottom, reaction solution is heated to 60 DEG C,
The tetrahydrofuran solution of acetophenone is added dropwise in reaction solution dropwise again, the sodium hydride：Methyl benzoate：Mole of acetophenone
Than for 2:1.2:1, the reaction solution h of back flow reaction 24 under a nitrogen；After reaction terminates, extract and 1- (4- bromines are made through column chromatography for separation
Phenyl) -1,3- propyl benzene -1,3- diketone；
By 4- triphenylamine boric acid：1- (4- bromophenyls) -1,3- propyl benzene -1,3- diketone：Potassium carbonate：The mol ratio of palladium is 2:1:
1.5:0.1 ratio feeds intake into two mouthfuls of flasks of round bottom, adds volume ratio as 3:1 ethanol-water mixed solution, backflow；
Extraction is made through column chromatography for separationβ- diketone assistant ligand；
(2) complex synthesizes
Into two mouthfuls of flasks of round bottom in molar ratio 1:1.2 add Platinous Potassium Chloride and 2- phenylpyridines, add volume ratio as 3:1
Ethylene glycol monoethyl ether and water mixed solution, nitrogen protection under in 105 DEG C reaction, reaction terminate after reaction solution is transferred to
In single necked round bottom flask, dichloro bridge intermediate product is obtained after vacuum revolving；Add sodium carbonate,β- diketone assistant ligand and second two
Alcohol list ether, the 2- phenylpyridines：β- diketone assistant ligand：The mol ratio of sodium carbonate is 0.24:0.6:1, under nitrogen protection
In 105 DEG C of h of magnetic agitation 24, reaction terminates rear vacuum revolving, through column chromatography for separation, obtains containing triphenylamineβ- diketone aids in
Part-platinum complex.
It is described containing triphenylamineβ- diketone assistant ligand-platinum complex is used as oxygen responsive probe OSPs.
The beneficial effects of the invention are as follows：It is this based on containing triphenylamineβ- diketone assistant ligand-platinum complex is easily prepared,
Synthesized by 2- phenylpyridines with through parabromoacetophenone, methyl benzoate and 4- triphenylamine boric acidβThe common network of-diketone assistant ligand
Platinum ion is closed to be formed.The platinum complex has good oxygen sensitivity, complete from 100% nitrogen to 100% oxygen, phosphorescence
Complete be quenched only needs 6.5 s；From 100% oxygen to 100% nitrogen, phosphorescence recovers to need 34.3 s, shows that platinum complex oxygen passes
Sense film has good phosphorescence quenching and the invertibity recovered；Can be to be supervised online in 0-100% oxygen concentration range in volume ratio
Oxygen determination gas concentration.
Brief description of the drawings
Fig. 1 is platinum complex in CH2Cl2Under ultraviolet/visible absorption spectra figure.
Fig. 2 is platinum complex in CH2Cl2Under launching light spectrogram.
Fig. 3 is platinum complex in ethyl cellulose（EC）Launching light spectrogram on film.
Fig. 4 is the dynamic phosphorescence response curve (support material of platinum complex the oxygen sensing film：EC).
Fig. 5 is the reversibility test curve (support material of platinum complex the oxygen sensing film：EC).
Embodiment
Embodiment 1 is containing triphenylamineβThe synthesis of-diketone assistant ligand-platinum complex
The specific synthesis step of the platinum complex is as follows：
(1) β- diketone assistant ligand synthesizes：Rapidly join sodium hydride (10 mmol), tetrahydrochysene successively into two mouthfuls of flasks of round bottom
Furans (20 mL) and methyl benzoate (6 mmol), 60 DEG C are heated to by reaction solution, then, with constant pressure funnel by benzene second
The tetrahydrofuran solution (20 mL) of ketone (5 mmol) is added dropwise in reaction solution dropwise, the reaction solution h of back flow reaction 24 under a nitrogen.
After reaction terminates, reaction solution is poured into water, pH value is adjusted to pH=7 with hydrochloric acid.Mixed liquor is extracted with ethyl acetate（30 mL
× 3）, merge organic phase, 1- (4- bromophenyls) -1,3- propyl benzene -1,3- diketone be made through column chromatography for separation.To two mouthfuls of burnings of round bottom
4- triphenylamines boric acid (2 mmol), 1- (4- bromophenyls) -1,3- propyl benzene -1,3- diketone (1 mmol), carbonic acid are sequentially added in bottle
Potassium (1.5 mmol), volume ratio 3:1 mL of ethanol-water mixed solution 16 and palladium (0.1 mmol).In reflux state
Lower progress Suzuki cross-coupling reactions, reaction process is tracked by thin-layered chromatography.After the completion of reaction, saturation is added to mixed liquor
The mL of saline solution 15, is extracted with ethyl acetate（15 mL × 3）, merging is organic through column chromatography for separation, is madeβ- diketone auxiliary is matched somebody with somebody
Body.
(2) complex synthesizes：Platinous Potassium Chloride (0.2 mmol), 2- phenylpyridines are added into two mouthfuls of flasks of round bottom
The mL water mixed solutions of (0.24 mmol) and 6 mL ethylene glycol monoethyl ethers/2, in 105 DEG C of magnetic agitations 24 under nitrogen protection
Reaction solution is transferred in single necked round bottom flask by h, reaction after terminating, and dichloro bridge intermediate product is obtained after vacuum revolving.To single port
The dichloro bridge intermediate product that adds to obtain in round-bottomed flask, sodium carbonate (1.0 mmol),β- diketone assistant ligand (0.6 mmol)
And 6 mL ethylene glycol monoethyl ethers, in 105 DEG C of h of magnetic agitation 24 under nitrogen protection, reaction terminates rear vacuum revolving, through column chromatography
Separation, is obtained containing triphenylamineβ- diketone assistant ligand-platinum complex.
Embodiment 2 is containing triphenylamineβThe spectrum property of-diketone assistant ligand-platinum complex
Fig. 1 is that beta-diketon assistant ligand-platinum complex concentration containing triphenylamine is 10-5Ultraviolet/visible absorbance that mol/L is obtained
Spectrogram, absorbing wavelength are 260 nm (2.81), 279 nm (2.36), 323 nm (1.37), 359 nm (1.59),
377 nm (1.36).Fig. 2 is platinum complex in organic solvent CH2Cl2Under launching light spectrogram, wherein= 559 nm；Figure
3 be platinum complex in ethyl cellulose（EC）Launching light spectrogram on film, wherein= 541 nm；Compared in CH2Cl2It is molten
18 nm of maximum emission wavelength blue shift in liquid on EC films.
Embodiment 3 is containing triphenylamineβThe oxygen Application in Sensing of-diketone assistant ligand-platinum complex
Platinum complex is carried on ethyl cellulose（EC）Oxygen sensitivity method of testing in film：At room temperature, 9.95 mg carriers are weighed
Material EC is dissolved in 900 μ L CH2Cl2Solution, 100 μ L concentration are added after being completely dissolved as 0.5 mg/mL platinum complexes
CH2Cl2Solution.Take the above-mentioned μ L of mixed solution 100 to be evenly coated on circular non-opaque quartz plate (r=0.7 cm), treat that solvent is slow
Volatilization, obtain oxygen sensing EC films (load capacity of platinum complex is 0.5 wt%).The oxygen sensing film is put into oxygen sensing flow cell,
Be passed through to it different volumes than O2/N2Mixed gas, coordinated using F-7000 XRFs test load in the platinum on EC films
The emission spectrum of thing.Fig. 4 is the dynamic phosphorescence response curve of platinum complex the oxygen sensing film, and it shows, containing triphenylamineβ- diketone
The oxygen sensing film prepared by assistant ligand-platinum complex can be in 0-100% oxygen concentration range in volume ratio to oxygen sensitive
Monitor oxygen concentration on-line.Fig. 5 is the reversibility test curve of platinum complex the oxygen sensing film, from 100% nitrogen to 100% oxygen
Gas, phosphorescence is quenched completely only needs 6.5 s；From 100% oxygen to 100% nitrogen, phosphorescence recovers to need 34.3 s, shows that platinum is matched somebody with somebody
Compound the oxygen sensing film has test invertibity well.
Claims (3)
1. containing triphenylamineβ- diketone assistant ligand-platinum complex, it is characterised in that：Matched somebody with somebody by 2- phenylpyridine C^N type ring metals
What body synthesized with by parabromoacetophenone, methyl benzoate and 4- triphenylamine boric acidβ- diketone assistant ligand be complexed jointly platinum from
Son is formed, and its structure is as follows：
。
It is 2. according to claim 1 containing triphenylamineβThe preparation method of-diketone assistant ligand-platinum complex, its feature exist
In：The specific synthesis step of the platinum complex is as follows：
(1) β- diketone assistant ligand synthesizes
Sodium hydride, tetrahydrofuran and methyl benzoate are sequentially added into two mouthfuls of flasks of round bottom, reaction solution is heated to 60 DEG C,
The tetrahydrofuran solution of acetophenone is added dropwise in reaction solution dropwise again, the sodium hydride：Methyl benzoate：Mole of acetophenone
Than for 2:1.2:1, the reaction solution h of back flow reaction 24 under a nitrogen；After reaction terminates, extract and 1- (4- bromines are made through column chromatography for separation
Phenyl) -1,3- propyl benzene -1,3- diketone；
By 4- triphenylamine boric acid：1- (4- bromophenyls) -1,3- propyl benzene -1,3- diketone：Potassium carbonate：The mol ratio of palladium is 2:1:
1.5:0.1 ratio feeds intake into two mouthfuls of flasks of round bottom, adds volume ratio as 3:1 ethanol-water mixed solution, backflow；
Extraction is made through column chromatography for separationβ- diketone assistant ligand；
(2) complex synthesizes
Into two mouthfuls of flasks of round bottom in molar ratio 1:1.2 add Platinous Potassium Chloride and 2- phenylpyridines, add volume ratio as 3:1
Ethylene glycol monoethyl ether and water mixed solution, nitrogen protection under in 105 DEG C reaction, reaction terminate after reaction solution is transferred to
In single necked round bottom flask, dichloro bridge intermediate product is obtained after vacuum revolving；Add sodium carbonate,β- diketone assistant ligand and second two
Alcohol list ether, the 2- phenylpyridines：β- diketone assistant ligand：The mol ratio of sodium carbonate is 0.24:0.6:1, under nitrogen protection
In 105 DEG C of h of magnetic agitation 24, reaction terminates rear vacuum revolving, through column chromatography for separation, obtains containing triphenylamineβ- diketone aids in
Part-platinum complex.
It is 3. according to claim 1 containing triphenylamineβThe application of-diketone assistant ligand-platinum complex, it is characterised in that：
The platinum complex is used as the luminescent material for making lambda sensor.
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| CN103145763A (en) * | 2013-03-02 | 2013-06-12 | 大连理工大学 | Novel cyclometal ligand-platinum complex and preparation method and application thereof |
| CN104311602A (en) * | 2013-03-02 | 2015-01-28 | 大连理工大学 | Quinoline-based ring metal ligand-platinum complex as well as preparation method and application thereof |
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| CN103145763A (en) * | 2013-03-02 | 2013-06-12 | 大连理工大学 | Novel cyclometal ligand-platinum complex and preparation method and application thereof |
| CN104311602A (en) * | 2013-03-02 | 2015-01-28 | 大连理工大学 | Quinoline-based ring metal ligand-platinum complex as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHUN LIU ET AL.: "Novel triphenylamine-based cyclometalated platinum(II) complexes for efficient luminescent oxygen sensing", 《DYES AND PIGMENTS》 * |
| YANG XING ET AL.: "Photostable trifluoromethyl-substituted platinum(II) emitters for continuous monitoring of molecular oxygen", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
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