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[Ru(pic)₂(dmso)₂] 中的光触发亚砜异构化

Phototriggered sulfoxide isomerization in [Ru(pic)2(dmso)2].

作者信息

Rachford Aaron A, Petersen Jeffrey L, Rack Jeffrey J

机构信息

Department of Chemistry and Biochemistry, Athens, Ohio 45701, USA.

出版信息

Dalton Trans. 2007 Aug 14(30):3245-51. doi: 10.1039/b704205a. Epub 2007 May 31.

Abstract

We report the characterization and photochemistry of a simple ruthenium coordination complex containing only picolinate (pic) and dmso, which exhibits a large isomerization quantum yield (Phi(SS-->OO) = 0.50) in various solvents. The picolinate ligands of [Ru(pic)(2)(dmso)(2)] are in a cis arrangement so that the carboxylate oxygen of one pic ligand (O1) is trans to the pyridine of the second picolinate (N2). One dmso ligand (S1) is trans to a pyridine nitrogen (N1), while the second dmso (S2) is trans to a carboxylate oxygen (O3). The cyclic voltammetry, (1)H NMR, IR, and UV-vis spectroscopy data suggest that while both dmso ligands isomerize photochemically, only one dmso ligand isomerizes electrochemically. Isomerization quantum yields for each dmso ligand differ by an order of magnitude (Phi(SS-->SO) = 0.46 and Phi(SO-->OO) = 0.036). In agreement with previous results, the isomerization quantum yield for each dmso is dependent on the ligand that is trans to the dmso.

摘要

我们报道了一种仅含吡啶甲酸酯(pic)和二甲基亚砜(dmso)的简单钌配位络合物的表征及光化学性质,该络合物在各种溶剂中表现出较大的异构化量子产率(Φ(SS→OO) = 0.50)。[Ru(pic)₂(dmso)₂]的吡啶甲酸酯配体呈顺式排列,使得一个pic配体的羧酸根氧(O1)与第二个吡啶甲酸酯的吡啶(N2)呈反式。一个dmso配体(S1)与一个吡啶氮(N1)呈反式,而第二个dmso(S2)与一个羧酸根氧(O3)呈反式。循环伏安法、¹H NMR、红外光谱和紫外可见光谱数据表明,虽然两个dmso配体都发生光化学异构化,但只有一个dmso配体发生电化学异构化。每个dmso配体的异构化量子产率相差一个数量级(Φ(SS→SO) = 0.46和Φ(SO→OO) = 0.036)。与先前的结果一致,每个dmso的异构化量子产率取决于与dmso呈反式的配体。

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