Si-Hai Wu, H. Abruña, Yu‐Wu Zhong
Feb 1, 2012
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Journal
Organometallics
Abstract
The reaction of 2,3-di(2-pyridyl)-5,6-diphenylpyrazine (dpdpz) with Re(CO)5Cl in acetonitrile or toluene afforded mono-Re and bis-Re complexes [Re(CO)3Cl-dpdpz] and [Re(CO)3Cl-dpdpz-Re(CO)3Cl], respectively. A heterodinuclear complex [Ru(bpy)2-dpdpz-Re(CO)3Cl](PF6)2 could be prepared by the reaction of [Re(CO)3Cl-dpdpz] with Ru(bpy)2Cl2 or the reaction of Re(CO)5Cl with a previously reported mono-Ru complex [Ru(bpy)2-dpdpz](PF6)2 in moderate yields. Surprisingly, the reaction of [Re(CO)3Cl-dpdpz] or [Re(CO)3Cl-dpdpz-Re(CO)3Cl] with Ru(tpy)Cl3 in the presence of AgOTf both afforded an asymmetric bis-Ru complex [Ru(tpy)-dpdpz-RuCl(tpy)](PF6)2. The solid-state structures of [Re(CO)3Cl-dpdpz-Re(CO)3Cl] and [Ru(tpy)-dpdpz-RuCl(tpy)](PF6)2 were determined by single-crystal X-ray analysis. The electrochemical, absorption, and emission properties of these compounds were studied by cyclic voltammetric and spectroscopic analyses. In addition, DFT calculations were carried out to aid in the interpretation of these e...