Control of Metal Arrays Based on Heterometallics Masquerading in Heterochiral Aggregations of Chiral Clothespin-Shaped Complexes
Heterometal arrays in molecular aggregations were obtained by the spontaneous and ultrasound‐induced gelation of organic liquids containing the chiral, clothespin‐shaped trans‐bis(salicylaldiminato) d8 transition‐metal complexes 1. Heterometallic mixtures of complexes 1 a (Pd) and 1 b (Pt) underwent...
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Published in | Chemistry : a European journal Vol. 21; no. 37; pp. 12927 - 12939 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
Weinheim
WILEY-VCH Verlag
07.09.2015
WILEY‐VCH Verlag Wiley Subscription Services, Inc |
Subjects | |
Online Access | Get full text |
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Summary: | Heterometal arrays in molecular aggregations were obtained by the spontaneous and ultrasound‐induced gelation of organic liquids containing the chiral, clothespin‐shaped trans‐bis(salicylaldiminato) d8 transition‐metal complexes 1. Heterometallic mixtures of complexes 1 a (Pd) and 1 b (Pt) underwent strict heterochiral aggregation entirely due to the organic shell structure of the clothespin shape, with no effect of the metal cores. This phenomenon provides an unprecedented means of generating highly controlled heterometallic arrangements such as alternating sequences [(+)‐Pd(−)‐Pt(+)‐Pd(−)‐Pt⋅⋅⋅] as well as a variety of single metal‐enriched arrays (e.g., [(+)‐Pt(−)‐Pd(+)‐Pd(−)‐Pd(+)‐Pd(−)‐Pd⋅⋅⋅] and [(+)‐Pd(−)‐Pt(+)‐Pt(−)‐Pt(+)‐Pt(−)‐Pt⋅⋅⋅]) upon the introduction of an optically active masquerading unit with a different metal core in the heterochiral single‐metal sequence. The present method can be applied to form various new aggregates with optically active Pd and Pt units, to allow 1) tuning of the gelation ultrasound sensitivity based on the different hearing abilities of the metal units; 2) aggregation‐induced chirality transfer between heterometallic species; and 3) aggregation‐induced chirality enhancement. A mechanistic rationale is proposed for these molecular aggregations based on the molecular structures of the units and the morphologies of the aggregates.
Undercover control: Heterometallic arrays, ultrasound responsiveness, and supramolecular chirality in molecular aggregation can be precisely controlled by the gelation of organic liquids containing the chiral, clothespin‐shaped trans‐bis(salicylaldiminato) d8 transition‐metal complexes (see figure). |
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Bibliography: | istex:60CFB0E3A21396AF26855D15FBD993F2503EB2F0 Grant-in-Aid for Scientific Research ArticleID:CHEM201500996 ark:/67375/WNG-DBG5CP0K-7 Japan Society for the Promotion of Science ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0947-6539 1521-3765 |
DOI: | 10.1002/chem.201500996 |