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手性凹型 9,9'-螺二芴衍生双(吡啶)配体构筑的金属超分子菱形的自组装。

Self-assembly of metallosupramolecular rhombi from chiral concave 9,9'-spirobifluorene-derived bis(pyridine) ligands.

机构信息

University of Bonn, Kekulé-Institute of Organic Chemistry and Biochemistry, Gerhard-Domagk-Str. 1, D-53121 Bonn, Germany.

Department of Chemistry, Nanoscience Center, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland.

出版信息

Beilstein J Org Chem. 2014 Feb 18;10:432-41. doi: 10.3762/bjoc.10.40. eCollection 2014.

Abstract

Two new 9,9'-spirobifluorene-based bis(4-pyridines) were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp)2M2L2] rhombi with cis-protected (dppp)Pd and (dppp)Pt ions. The self-assembly process of the racemic ligand preferably occurs in a narcissistic self-recognising manner. Hence, a mixture of all three possible stereoisomers (dppp)2M2{(R)-L}24, (dppp)2M2{(S)-L}24, and (dppp)2M2{(R)-L}{(S)-L}4 was obtained in an approximate 1.5:1.5:1 ratio which corresponds to an amplification of the homochiral assemblies by a factor of approximately three as evidenced by NMR spectroscopy and mass spectrometry. The racemic homochiral assemblies could also be characterised by single crystal X-ray diffraction.

摘要

两种新的基于 9,9'-螺二芴的双(4-吡啶基)以对映纯和一种外消旋形式合成。这些配体作为凹面模板,与顺式保护的 (dppp)Pd(dppp)Pt 离子形成具有金属超分子 [(dppp)2M2L2] 菱形。外消旋配体的自组装过程优选以自恋式自我识别方式发生。因此,获得了三种可能的立体异构体的混合物 (dppp)2M2{(R)-L}24、(dppp)2M2{(S)-L}24 和 (dppp)2M2{(R)-L}{(S)-L}4,其比例约为 1.5:1.5:1,这对应于通过 NMR 光谱和质谱证实的同手性组装的放大倍数约为三倍。外消旋同手性组装也可以通过单晶 X 射线衍射进行表征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/36bd/3943293/8b520311d989/Beilstein_J_Org_Chem-10-432-g007.jpg

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