Bimetallic Iridium(III) Complexes Consisting of Ir(ppy)2 Units (ppy = 2-Phenylpyridine) and Two Laterally Connected N<
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- 作者：Audrey Auffrant ; Andrea Barbieri ; Francesco Barigelletti ; Jé ; rô ; me Lacour ; Pierre Mobian ; Jean-Paul Collin ; Jean-Pierre Sauvage ; Barbara Ventura
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：August 20, 2007
- 年：2007
- 卷：46
- 期：17
- 页码：6911 - 6919
- 全文大小：259K
- 年卷期：v.46,no.17(August 20, 2007)
- ISSN：1520-510X
文摘
Reaction of the precursor complex Ir2(ppy)4Cl2 (ppy = 2-phenylpyridine) with the bridging ligand 3,8-dipyridyl-4,7-phenanthroline (L) affords, in 94% yield, the cyclometalated iridium dinuclear complex [(ppy)2Ir(
r.gif">-L)Ir(ppy)2]2+ (12+)as a mixture of three stereoisomers. This mixture consists of a meso form 
rs/Delta.gif" BORDER=0 >,
r.gif"> and a racemic form (enantiomericpair rs/Delta.gif" BORDER=0 >,rs/Delta.gif" BORDER=0 > and r.gif">,r.gif">) in the ratio 1:1.5. Single-crystal X-ray characterization of the perchlorate salt of the meso formreveals (i) the distortion of the bridging ligand from the planarity and (ii) the location of the two iridium subunitsabove and below the medium plane of the bridging ligand. Ion-pair chromatography with rs/Delta.gif" BORDER=0 >-TRISPHAT anion(TRISPHAT = tris(tetrachlorobenzenediolato)phosphate(V)) as resolving anion permits the separation of the threestereoisomers. The 1H NMR spectroscopic analysis of each fraction indicates high diastereomeric purity. Electroniccircular dichroism properties and comparison with literature data establish their absolute configuration. The absorptionand emission properties of the three stereoisomers show only very small variations. The anisotropic properties canbe interpreted as distinct interactions of the isomers with the chiral resolving rs/Delta.gif" BORDER=0 >-TRISPHAT anion.
r.gif">-L)Ir(ppy)2]2+ (12+)as a mixture of three stereoisomers. This mixture consists of a meso form rs/Delta.gif" BORDER=0 >,r.gif"> and a racemic form (enantiomericpair rs/Delta.gif" BORDER=0 >,rs/Delta.gif" BORDER=0 > and r.gif">,r.gif">) in the ratio 1:1.5. Single-crystal X-ray characterization of the perchlorate salt of the meso formreveals (i) the distortion of the bridging ligand from the planarity and (ii) the location of the two iridium subunitsabove and below the medium plane of the bridging ligand. Ion-pair chromatography with rs/Delta.gif" BORDER=0 >-TRISPHAT anion(TRISPHAT = tris(tetrachlorobenzenediolato)phosphate(V)) as resolving anion permits the separation of the threestereoisomers. The 1H NMR spectroscopic analysis of each fraction indicates high diastereomeric purity. Electroniccircular dichroism properties and comparison with literature data establish their absolute configuration. The absorptionand emission properties of the three stereoisomers show only very small variations. The anisotropic properties canbe interpreted as distinct interactions of the isomers with the chiral resolving rs/Delta.gif" BORDER=0 >-TRISPHAT anion.