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https://hdl.handle.net/2440/116075
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Type: | Journal article |
Title: | Geometric complementarity in assembly and guest recognition of a bent heteroleptic cis-[Pd₂LA₂LB₂] coordination cage |
Author: | Bloch, W.M. Abe, Y. Holstein, J.J. Wandtke, C.M. Dittrich, B. Clever, G.H. |
Citation: | Journal of the American Chemical Society, 2016; 138(41):13750-13755 |
Publisher: | American Chemical Society |
Issue Date: | 2016 |
ISSN: | 0002-7863 1520-5126 |
Statement of Responsibility: | Witold M. Bloch, Yoko Abe, Julian J. Holstein, Claudia M. Wandtke, Birger Dittrich and Guido H. Clever |
Abstract: | 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 [Pd2LA2LB2]4+ coordination cage achieved through the geometric complementarity of two carefully designed ligands, LA and LB. With Pd(II) cations as rigid nodes, the pure distinctly angular components readily form homoleptic cages, a [Pd2LA4]4+ strained helical assembly and a [Pd4LB8]8+ 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-[Pd2LA2LB2]4+ 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 [Pd2LA2LB2]4+ 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-[Pd2LA2LB2]4+ species. The robust nature of the cis-[Pd2LA2LB2]4+ 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 [Pd2L4] cages and opens up possibilities of introducing multiple functionalities into a single self-assembled architecture. |
Rights: | © 2016, American Chemical Society |
DOI: | 10.1021/jacs.6b08694 |
Published version: | http://dx.doi.org/10.1021/jacs.6b08694 |
Appears in Collections: | Aurora harvest 3 Chemistry publications |
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