title: Study on the synthesis, characterization, photophysical performance and oxygen-sensing behavior of a luminescent Cu(I) complex with large conjugation plane.
abstract: In this paper, a diamine ligand of dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) and its corresponding Cu(I) complex with triphenylphosphine (PPh(3)) as the phosphorous ligand are synthesized. Full characterization on [Cu(DPPZ)(PPh(3))(2)]BF(4), including NMR, elemental analysis and single crystal analysis, confirms its molecular identity. Upon photon excitation, the emission of [Cu(DPPZ)(PPh(3))(2)]BF(4) owns a long excited state lifetime of ∼6 μs and shows a maximum intensity at 616 nm, under pure N(2) atmosphere. Theoretical calculation on [Cu(DPPZ)(PPh(3))(2)]BF(4) single crystal suggests that the excited state has a triplet metal-to-ligand-charge-transfer character. By embedding [Cu(DPPZ)(PPh(3))(2)]BF(4) into a polymer supporting matrix of polystyrene, the emission signal is found to be sensitive towards varying oxygen concentrations, with a maximum sensitivity of 3.78. We attribute this sensitivity to the large conjugation plane in DPPZ ligand which can increase the population of excited state electrons and favor the oxygen attack on [Cu(DPPZ)(PPh(3))(2)]BF(4) excited state. Due to the porous structure of nanofibrous polystyrene matrix, a short response time of ∼16 s towards molecular oxygen is also observed with stable quenching signal.
authors.affiliation: Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China.
authors.forename: Wensheng
authors.initials: W
authors.lastname: Yang
authors.forename: Wan
authors.initials: W
authors.lastname: Yang
authors.forename: Weisheng
authors.initials: W
authors.lastname: Liu
authors.forename: Wenwu
authors.initials: W
authors.lastname: Qin
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004583:Electrons; D008163:Luminescent Measurements; D008855:Microscopy, Electron, Scanning; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry*; D010777:Photochemistry; D013056:Spectrophotometry, Ultraviolet; D013997:Time Factors
chemical_list: D056831:Coordination Complexes; D003300:Copper; D010100:Oxygen