Synthesis, Characterization and Luminescent Properties of Two Copper(Ⅰ) Complexes Based on 2,2'-Biquinoline and Phosphorous Ligand

摘要

Three new copper(Ⅰ) complexes,namely [Cu(DPEphos)(Biq)]CF3SO3 (1) and [Cu(PPh3)2(Biq)]CF3SO3 (2) and [Cu(PPh3)2(Biq)]ClO4 (3) (DPEphos =bis[2-(diphenylphosp hino)phenyl]ether,PPh3 =triphenylphosphine and Biq =2,2'-biquinoline),are synthesized and characterized by IR,1H NMR,31p NMR,fluorescence spectra and terahertz time-domain spectroscopy (THz-TDS).Complex 1 crystallizes in triclinic,space group P(1) with a =12.6997(5),b =13.2813(5),c =15.3593(6) (A),a =80.211(3)°,β =88.752(3)°,γ =70.113(3)°,V=2398.85(15) (A)3,C55H41.2CuF3N2O4.6P2S,Mr =1018.27,Z =2,Dc=1.410 g/cm3,F(000) =1048,μ =0.628 mm-1,the final R =0.0450 and wR =0.1105 for 9419 observed reflections (Ⅰ ＞ 2σ(Ⅰ)).Complex 2 crystallizes in monoclinic,space group C2/c with a =19.9961(7),b =15.9774(5),c =17.7908(6) (A),β =119.758(4)°,V=4982.8(3) (A)3,C56.47H47.88CuF3N2O4.47P2S,Mr=1040.54,Z =4,Dc=1.387 g/cm3,F(000) =2154,μ =0.606 mm-1,the final R =0.0430 and wR =0.1218 for 4897 observed reflections (Ⅰ ＞ 2σ(Ⅰ)).Complex 3 crystallizes in monoclinic,space group C2/c with a =19.7534(8),b =15.0797(5),c =17.8097(7) (A),β =116.400(5)°,V =4751.8(3) (A)3,C56H45ClCuN3O4P2,Mr =984.88,Z=4,Dc=1.377 g/cm3,F(000) =2040,μ =0.635 mm-1,the final R =0.0731 and wR =0.2180 for 4670 observed reflections (Ⅰ ＞ 2σ(Ⅰ)).In the emission spectra,shifts of emission peak are derived from ligand-centered (π-π*) transition.