Geometric Complementarity in Assembly and Guest Recognition of a Bent Heteroleptic cis-[PdLL] Coordination Cage.
Due to the inherent difficulties in achieving a defined and exclusive formation of multicomponent assemblies against entropic predisposition, we present the rational assembly of a heteroleptic [PdLL] coordination cage achieved through the geometric complementarity of two carefully designed ligands,...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 41; pp. 13750 - 13756 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
10/19/2016
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=119357033&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 119357033 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/19/2016 vid: 138 iid: 41 pid: 997 pub: American Chemical Society artinfo: ui: 119357033 10.1021/jacs.6b08694 ppf: 13750 ppct: 6 formats: tig: atl: Geometric Complementarity in Assembly and Guest Recognition of a Bent Heteroleptic cis-[PdLL] Coordination Cage. aug: au: Bloch, Witold M. Abe, Yoko Holstein, Julian J. Wandtke, Claudia M. Dittrich, Birger Clever, Guido H. affil: Faculty of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, 44227 Dortmund, Germany Institute for Inorganic Chemistry, Georg-August University Göttingen, Tammannstraße 4, 37077 Göttingen, Germany Institute for Inorganic Chemistry and Structural Chemistry, Heinrich-Heine University Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany su: Palladium Biocomplexity Thermodynamics Biological systems Heteroleptic compounds sug: subj: Palladium Biocomplexity Thermodynamics Biological systems Heteroleptic compounds ab: Due to the inherent difficulties in achieving a defined and exclusive formation of multicomponent assemblies against entropic predisposition, we present the rational assembly of a heteroleptic [PdLL] coordination cage achieved through the geometric complementarity of two carefully designed ligands, L and L. With Pd(II) cations as rigid nodes, the pure distinctly angular components readily form homoleptic cages, a [PdL] strained helical assembly and a [PdL] box-like structure, both of which were characterized by X-ray analysis. Combined, however, the two ligands could be used to cleanly assemble a cis-[PdLL] cage with a bent architecture. The same self-sorted product was also obtained by a quantitative cage-to-cage transformation upon mixing of the two homoleptic cages revealing the [PdLL] assembly as the thermodynamic minimum. The structure of the heteroleptic cage was examined by ESI-MS, COSY, DOSY, and NOESY methods, the latter of which pointed toward a cis-conformation of ligands in the assembly. Indeed, DFT calculations revealed that the angular ligands and strict Pd(II) geometry strongly favor the cis-[PdLL] species. The robust nature of the cis-[PdLL] cage allowed us to probe the accessibility of its cavity, which could be utilized for shape recognition toward stereoisomeric guests. The ability to directly combine two different backbones in a controlled manner provides a powerful strategy for increasing complexity in the family of [PdL] cages and opens up possibilities of introducing multiple functionalities into a single self-assembled architecture. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2016 holdings: @attributes: islocal: N |
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