Faculty of Physics, St. Petersburg State University, St. Petersburg, Russia.
J Phys Chem A. 2011 Dec 22;115(50):14235-42. doi: 10.1021/jp2062354. Epub 2011 Nov 28.
Emission, excitation spectra, quantum yields, and emission lifetimes are reported for the mixed-ligand, bis(2.2'-bipyridine)ruthenium(II) complexes, cis-Ru(bpy)(2)(PPh(3))X with X = Cl(-), Br(-), CN(-), and NO(2)(-) (n = 1) and pyridine (py), 4-aminopyridine (NH(2)py), 4,4'- bipyridine (4,4'-bpy), NH(3), and MeCN (n = 2) in EtOH-MeOH, 4:1 (v:v), at 77 K. Radiative, k(r), and nonradiative, k(nr), decay rate constants were determined for the series of complexes, and a linear dependence of ln k(nr) on E(00), with E(00) being the 0-0 energy gap determined by emission spectral fitting, was obtained with a slope of -(0.6 ± 0.1) × 10(-3). On the basis of emission quantum yields and apparent k(r) values, possible metal-to-ligand charge-transfer (MLCT) deactivation by direct population of excited (1)dd states from initially excited (1)MLCT states is discussed.
报告了混合配体双（2,2'-联吡啶）钌（II）配合物 cis-[Ru（bpy）（2）（PPh 3 ）X]（n+）（X = Cl-，Br-，CN-和 NO 2 -）（n = 1）和吡啶（py），4-氨基吡啶（NH 2 py），4,4'-联吡啶（4,4'-bpy），NH 3 和 MeCN（n = 2）在 EtOH-MeOH，4：1（v：v）中的发射，激发光谱，量子产率和发射寿命在 77 K。测定了一系列配合物的辐射 k（r）和非辐射 k（nr）衰减速率常数，并通过发射光谱拟合得到了 ln k（nr）与 E（00）的线性关系，其中 E（00）是通过发射光谱拟合确定的 0-0 能隙，斜率为-(0.6 ± 0.1) × 10（-3）。根据发射量子产率和表观 k（r）值，讨论了最初激发的（1）MLCT 态直接向激发的（1）dd 态的配体电荷转移（MLCT）失活。
