Ishow Eléna, Gourdon André, Launay Jean-Pierre, Lecante Pierre, Verelst Marc, Chiorboli Claudio, Scandola Franco, Bignozzi Carlo-Alberto
CEMES-CNRS UPR 8011, BP 4347, 29 Rue Jeanne Marvig, 31055 Toulouse, France, and Dipartimento di Chimica, Centro di Reattività e Catalisi CNR, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy.
Inorg Chem. 1998 Jul 13;37(14):3603-3609. doi: 10.1021/ic9715815.
The tetranuclear ruthenium complex {Ru(tpphz)Ru(bpy)(2)}(8+), where tpphz is tetrapyrido[3,2-a:2',3'-c:3",2"-h:2"',3"'-j]phenazine, has been synthesized by reaction of Ru(tpphz)(3) with [Ru(bpy)(2)Cl(2)] and by reaction of Ru(bpy)(2)(tpphz) with [Ru(DMSO)(4)Cl(2)]. The large distance between the chiral centers allows full (1)H NMR interpretation despite the mixture of eight stereoisomers. The tetranuclear complex was further characterized by electrospray mass spectrometry and by the wide-angle X-ray scattering technique, which confirmed the starburst geometry. The photophysical properties of the tetranuclear complex in acetonitrile were studied and compared with those of Ru(tpphz)(3) (1 x 10(-)(4) M acidic solution) and (bpy)(2)Ru(tpphz)Ru(bpy)(2) model molecules. The tetranuclear complex gives rise to a single emission, attributed to metal-to-ligand charge-transfer states involving peripheral Ru centers and tpphz bridging ligands.
四核钌配合物{Ru(tpphz)Ru(bpy)(2)}(8+)，其中tpphz为四吡啶并[3,2 - a:2',3'-c:3",2"-h:2"',3"'-j]吩嗪，通过Ru(tpphz)(3)与[Ru(bpy)(2)Cl(2)]反应以及Ru(bpy)(2)(tpphz)与[Ru(DMSO)(4)Cl(2)]反应合成。手性中心之间的距离较大，尽管存在八种立体异构体的混合物，但仍可进行完整的(1)H NMR解析。通过电喷雾质谱和广角X射线散射技术对四核配合物进行了进一步表征，证实了其星爆几何结构。研究了四核配合物在乙腈中的光物理性质，并与Ru(tpphz)(3)（1×10(-)(4) M酸性溶液）和(bpy)(2)Ru(tpphz)Ru(bpy)(2)模型分子的光物理性质进行了比较。四核配合物产生单一发射，归因于涉及外围Ru中心和tpphz桥连配体的金属到配体电荷转移态。
