Synthesis, photophysical and theoretical studies of luminescent silver(I)-copper(I) alkynyl-diphosphine complexes.
The novel heterometallic aggregates [Ag(8)Cu(2)(C(2)C(6)H(4)X)(6)(PPh(2)C(6)H(4)PPh(2))(6)][PF(6)](4) (X = H, 1; OMe, 2; NMe(2), 3) were prepared by the self-assembly reactions starting from simple precursors. These compounds consist of the central [Ag(6)Cu(2)(C(2)C(6)H(4)X)(6)](2+) clusters capped by two tripodal fragments [Ag(diphosphine)(3)](+). The solid state structures of complexes 1 and 3 have been determined by X-ray crystallographic studies, and NMR spectroscopy confirmed that the compounds remain intact in solution. In solution such as CH(3)CN, complexes 1-3 show a weak to moderate room-temperature phosphorescence in the blue region with a maximum quantum yield of 0.038 (2), while strong phosphorescence was recorded in the solid film of with a quantum yield of 0.26. Photophysical experiments revealed a relatively small effect of luminescence quenching by O(2) for 1, but more prominent quenching for 2 and 3 in solution. Computational approaches are in good agreement with the experimental data, supporting the proposed structural motif, and provide an additional insight into the electronic properties of these compounds to rationalize the different behavior of 1 compared to 2 and 3.
Koshevoy
Igor O
IO
University of Joensuu, Joensuu, 80101, Finland. igor.koshevoy@joensuu.fi
Karttunen
Antti J
AJ
Lin
Yi-Chih
YC
Lin
Chao-Chen
CC
Chou
Pi-Tai
PT
Tunik
Sergey P
SP
Haukka
Matti
M
Pakkanen
Tapani A
TA
D000480:Alkynes / Q000737:chemistry; D003198:Computer Simulation; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D049449:Luminescence; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D010777:Photochemistry; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry; D013237:Stereoisomerism
D000480:Alkynes; D009942:Organometallic Compounds; D010720:Phosphines; D012834:Silver; D003300:Copper