The crystal structures and electronic properties of three new [Cu(bipy)2(ONO)][Y] complexes. The structural pathway of the [Cu(bipy)2(ONO)][Y] series of complexes. Further insights into the Pseudo Jahn–Teller model
✍ Scribed by Brian Murphy; George Roberts; Suresh Tyagi; Brian J Hathaway
- Publisher
- Elsevier Science
- Year
- 2004
- Tongue
- English
- Weight
- 295 KB
- Volume
- 698
- Category
- Article
- ISSN
- 0022-2860
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✦ Synopsis
The crystal structures of three new [Cu(bipy)
, 2, and [I] 2 , 3, have been determined at room temperature by single crystal X-ray analysis. All three complexes involve a CuN 4 O 2 chromophore, with an asymmetric cis-distorted octahedral (CDO) stereochemistry. The stereochemistries of 1, 2 and 3, are compared with three other cation distortion isomers, 5, and [HSO 4 ] 2 , 6, by scatter plot analysis to characterise a possible structural pathway involving the [Cu(bipy) 2 (ONO)] þ cation only, accounting for the occurrence of discrete a 3 angles and right-pointing arrowhead structures, features which are not readily accounted for by the original tris-chelate Jahn -Teller/Pseudo Jahn-Teller (JT/PJT) model. Further insights into the stereochemistry of the CuN 4 O 2 chromophore as an independent PJT system involving vibronic coupling between the degenerate 2 A type ground state in low point group symmetry (C 2 or C 1 symmetry) and a corresponding excited state are presented. This paper raises some question marks about the original PJT model of CDO chromophores which do not take into account the experimental observation of the ranges of the a 3 discrete angles or the arrowhead fine structure of the data, within the range of the cluster of a 3 angles.