Observation of Long-Range Vicinal Effect in Chiral Cu(II)-Cr(VI) or Cu(II)-W(VI) Bimetallic Coordination Polymers 英文参考文献.docVIP

Polymers 2011, 3, 1029-1035; doi:10.3390/polym3031029 OPEN ACCESS polymers ISSN 2073-4360 /journal/polymers Communication Observation of Long-Range Vicinal Effect in Chiral Cu(II)-Cr(VI) or Cu(II)-W(VI) Bimetallic Coordination Polymers Naoshi Hayashi and Takashiro Akitsu * Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan * Author to whom correspondence should be addressed; E-Mail: akitsu@rs.kagu.tus.ac.jp; Tel.: +81-3-5228-8271; Fax: +81-3-5261-4631. Received: 13 May 2011; in revised form: 17 June 2011 / Accepted: 28 June 2011 / Published: 29 June 2011 Abstract: We have prepared some diastereomers of [CuL2][M2O7] (L is 1,2-diaminocyclohexane and its derivatives; M = Cr and W) bimetallic coordination polymers and confirmed their structural similarity and inner electronic states by means of XRD and XAS, respectively. For the first time, we have successfully observed distant vicinal effect of which the chiral source is only chiral organic ligands of [CuL2]2+ moieties (acting as ligand complex), while probe bands for solid state CD spectra are charge transfer (CT) bands of [M2O7]2? moieties (achiral complex) with the d0 electronic configuration. The new concept (interpretation) of this observation will be important for supramolecular chirality of coordination polymers built by ligand complexes. Keywords: chirality; copper; CD; XRD; XAS 1. Introduction Recently we have proposed a new concept of “supramolecular vicinal effect”, which is long-range induced chiroptical observation of an achiral unit from non-bonded (supramolecular assemblies) or weakly surrounded (host-guest co-crystal) chiral sources [1]. It is different to the normal vicinal effect (observation of CD bands in d-d region from chiral ligands through coordination bonds) [2,3] or  Polymers 2011, 3 1030 conventionally induced CD of many supramolecular a