The Research Of Designed Synthesis,Structure And Luminescence Sensing Properties Of Cuprous Complexes

Volatile Organic Compouns?VOC?can cause air pollution and potential safety hazards,so the research on VOC detection technology has great practical significance.Especially under the background that the public pay more and more attention to the air quality,there is an urgent need for efficient,safe and inexpensive technologies to complete the detection and evaluation of VOC in the air.There are various VOC detection methods currently being carried out,but there are still some problems such as difficulty in miniaturization and portability of the instrument,difficulty in real-time and in-situ detection,complicated detection process,high difficulty and over-specialization in detection operation,and secondary emission pollution.The discovery of the response of luminescent materials to VOC provides a new idea for VOC detection,because luminescence sensing detection is expected to have many advantages such as easy miniaturization of detection equipment,sensitive response,rapid detection,convenient in-situ real-time detection,no consumption and emission,etc.On account of these reasons,VOC luminescent sensing material are explored in this thesis based on cheap cuprous complexes.Through the molecular structure design of VOC luminescence sensing response,a series of cuprous complexes were synthesized.Based on the single crystal growth of the complex and the fabrication of the sensing film,the single crystal structure,spectrum and VOC luminescence sensing properties of the obtained material are studied in detail,the relationship between the structure and properties of the material is deeply discussed,and the optimization research of the luminescence sensing properties of the sensing film is attempted preliminarily.The specific contents are as follows:1.The design,synthesis,structure and luminescence sensing properties of three-coordinate cuprous complexes.Seven complexes 1-7?complex 1:[Cu?O-Anisyl₃P??2,2'-bipy?]PF₆;complex 2:[Cu?O-Anisyl₃P?₂?2,2'-bipy?]PF₆;complex3:[Cu?O-Anisyl₃P??2,2'-bipy??4-Mepy?]PF₆;complex4:[Cu?O-Anisyl₃P??2-QBO?]PF₆;complex 5:[Cu?O-Anisyl₃P?₂?2-QBO?]PF₆;complex6:[Cu?O-Anisyl₃P??2-QBI?]PF₆;complex 7:[Cu?O-Anisyl₃P??Phen?]PF₆?were designed and synthesized with bulky phosphine ligand Tri?o-anisyl?phosphine?O-Anisyl₃P?and diimine ligand of 2,2'-Bipyridine?2,2'-bipy?,4-Methylpyridine?4-Mepy?,2-?2-Quinoline?Benzoxazole?2-QBO?;2-?2-Quinoline?Benzimidazole?2-QBI?and o-Phenanthroline?Phen?.Among them,the four-coordinate complex containing two P ligands has higher luminescence intensity than the three-coordinate complex containing one P ligand.It is found that complex 1 has good luminescence sensing properties.In the VOC vapors of DMF,methylamine,triethylamine,methanol,n-butanol,acetonitrile,4-methylpyridine,3-phenylpyridine and2-phenylpyridine,complex 1 has significant response to 4-methylpyridine and3-phenylpyridine:a very bright blue-green emission(emission peak?_em=490 nm)can be observed after responding in 4-methylpyridine atmosphere;a very bright orange light emission(emission peak?_em=530 nm)can be observed after responding in 3-phenylpyridine atmosphere.And the response phenomenon can be clearly detected in a short time.It can be seen that complex 1 exhibits good selectivity and sensitivity for VOC luminescence sensing.2.The design,synthesis,structure and luminescence sensing properties of four-coordinate cuprous complexes containing volatile ligand.Two complexes 8-9?complex8:[Cu?POP??4-PBO??CH₃CN?]PF₆;complex9:[Cu₂?POP?₂?CH₃CN?₂?4,4'-bipy?]PF₆?were designed and synthesized with Bis?2-diphenylphosphinophenl?ether?POP?,4,4'-Bipyridine?4,4'-bipy?and2-?4-Pyridine?Benzoxazole?4-PBO?.It is found that complex 8 has good luminescence sensing properties.In the VOC vapors of DMF,methylamine,triethylamine,methanol,n-butanol,acetonitrile,4-methylpyridine,3-phenylpyridine and 2-phenylpyridine,complex 8 has significant response to DMF and3-phenylpyridine:a very bright blue emission(emission peak?_em=460 nm)can be observed after responding in DMF atmosphere;a very bright blue-green light emission(emission peak?_em=420 nm,550 nm)can be observed after responding in3-phenylpyridine atmosphere.And the response phenomenon can be clearly detected in a short time.It can be seen that complex 8 exhibits good selectivity,sensitivity and repeatability for VOC luminescence sensing.3.Design,synthesis,structure and sensing properties of cuprous luminescent complexes containing halogen and bulky phosphine ligands.Six complexes 10-15?complex 10:Cu?Xantphos?I;complex 11:Cu?Xantphos??3-PBO?I;complex 12:Cu?Xantphos??4-CNPy?I;complex 13:Cu₂?Xantphos??4-PBO?₂I₂;complex 14:Cu₂?BINAP?₂I₂;complex 15:Cu?PPh₃?₂?CH₃CN?I?were designed and synthesized by using 4,5-Bis?diphenylphosphino?-9,9-dimethylxanthene?Xantphos?or1.1'-Binaphthyl-2.2'-diphemyl phosphine?BINAP?as bulky phosphine ligands,2-?3-Pyridine?Benzoxazole?3-PBO?,4-Cyanopyridine?4-CNPy?and2-?4-Pyridine?Benzoxazole?4-PBO?as nitrogen ligands,and adding I^-ion.These cuprous iodide complexes show strong luminescence,which origins from?M+X?LCT excited states.It is found that complex 10 has good luminescence sensing properties.In the VOC vapors of DMF,methylamine,triethylamine,methanol,n-butanol,acetonitrile,4-methylpyridine,3-phenylpyridine and2-phenylpyridine,complex 10 has significant response to methylamine,4-methylpyridine and 3-phenylpyridine,exhibit different luminescence changes for different VOC:a very bright blue emission(emission peak?_em=410 nm,460 nm)can be observed after responding in methylamine atmosphere;a very bright blue-green light emission(emission peak?_em=490 nm)can be observed after responding in 4-methylpyridine atmosphere;a very bright yellow-green light emission(emission peak?_em=510 nm)can be observed after responding in3-phenylpyridine atmosphere.And the response phenomenon can be clearly detected in a short time.It can be seen that complex 10 exhibits good selectivity and sensitivity for VOC luminescence sensing.