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July 17, 2007Inorganic Chemistry

Bimetallic Iridium(III) Complexes Consisting of Ir(ppy)2 Units (ppy = 2-Phenylpyridine) and Two Laterally Connected N∧N Chelates as Bridge:  Synthesis, Separation, and Photophysical Properties

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Authors

AAAudrey AuffrantABAndrea BarbieriFBFrancesco Barigelletti

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Overview

Experimental study demonstrates efficient synthesis and chromatographic separation of bimetallic iridium(III) stereoisomers, indicating distinct chiral interactions despite uniform photophysics.

Key Points

  • To synthesize bimetallic iridium(III) complexes linked by a dipyridyl-phenanthroline bridge and isolate their individual stereoisomeric forms to investigate their structural and photophysical properties.
  • Reacted the precursor complex Ir2(ppy)4Cl2 with the bridging ligand 3,8-dipyridyl-4,7-phenanthroline to generate the dinuclear complex [(ppy)2Ir(mu-L)Ir(ppy)2]2+.
  • Determined solid-state structure via single-crystal X-ray diffraction of the meso perchlorate salt.
  • Separated stereoisomers via ion-pair chromatography using Delta-TRISPHAT as the chiral resolving anion, followed by 1H NMR and electronic circular dichroism spectroscopy to establish purity and absolute configuration.
  • Obtained the dinuclear iridium complex in 94% yield as a mixture of meso (Delta,Lambda) and racemic (Delta,Delta / Lambda,Lambda) forms in a 1:1.5 ratio.
  • Single-crystal X-ray analysis of the meso isomer revealed distortion of the bridging ligand from planarity with the iridium centers situated on opposite sides of the ligand plane.
  • Resolved all three stereoisomers with high diastereomeric purity, observing minimal variations in electronic absorption and emission spectra across the separate isomers.

Cite This Study

Auffrant et al. (2007) studied this question.

synapsesocial.com/papers/6a72e36c7cdbf433fe15482ehttps://doi.org/10.1021/ic700494e
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Also Consider

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