Assembling Quasi-enantiomeric Octahedral Complexes of Different Metals via Quasi-racemate Crystallization

Yanay Popowski; Israel Goldberg; Moshe Kol

doi:10.1002/chem.201505228

Assembling Quasi-enantiomeric Octahedral Complexes of Different Metals via Quasi-racemate Crystallization

Yanay Popowski, Israel Goldberg^*, Moshe Kol

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Aiming at a general methodology for binary co-assembly of complexes of different metals through quasiracemate crystallization, the hexadentate ligand 1 comprised of the chiral bipyrrolidine core and two bipyridine peripheral arms is introduced. Ligand 1 was found to bind in a fully diastereoselective and uniform mode around Zn^II, Fe^II and Cd^II giving coordinatively inert octahedral "chiral-at-metal" complexes with the Δ₄Λ₂/Λ₄Δ₂ wrapping mode. Equimolar mixtures of quasienantiomeric pairs of these complexes exhibited a clear tendency to pack as quasiracemates as was revealed from the crystallographic structures of [(R,R)-1-Zn](PF₆)₂/[(S,S)-1-Fe](PF₆)₂ and [(R,R)-1-Zn](PF₆)₂/[(S,S)-1-Cd](PF₆)₂, in an isomorphous fashion to that of the racemic compound [rac-1-Zn](PF₆)₂ in space group C2/c.

Original language	English
Pages (from-to)	5530-5533
Number of pages	4
Journal	Chemistry - A European Journal
Volume	22
Issue number	16
DOIs	https://doi.org/10.1002/chem.201505228
State	Published - 11 Apr 2016

Keywords

binary materials
bipyrrolidine
chiral ligands
hexadentate ligands
quasiracemate

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10.1002/chem.201505228

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abstract = "Aiming at a general methodology for binary co-assembly of complexes of different metals through quasiracemate crystallization, the hexadentate ligand 1 comprised of the chiral bipyrrolidine core and two bipyridine peripheral arms is introduced. Ligand 1 was found to bind in a fully diastereoselective and uniform mode around ZnII, FeII and CdII giving coordinatively inert octahedral {"}chiral-at-metal{"} complexes with the Δ4Λ2/Λ4Δ2 wrapping mode. Equimolar mixtures of quasienantiomeric pairs of these complexes exhibited a clear tendency to pack as quasiracemates as was revealed from the crystallographic structures of [(R,R)-1-Zn](PF6)2/[(S,S)-1-Fe](PF6)2 and [(R,R)-1-Zn](PF6)2/[(S,S)-1-Cd](PF6)2, in an isomorphous fashion to that of the racemic compound [rac-1-Zn](PF6)2 in space group C2/c.",

keywords = "binary materials, bipyrrolidine, chiral ligands, hexadentate ligands, quasiracemate",

author = "Yanay Popowski and Israel Goldberg and Moshe Kol",

note = "Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

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doi = "10.1002/chem.201505228",

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AU - Popowski, Yanay

AU - Goldberg, Israel

AU - Kol, Moshe

PY - 2016/4/11

Y1 - 2016/4/11

N2 - Aiming at a general methodology for binary co-assembly of complexes of different metals through quasiracemate crystallization, the hexadentate ligand 1 comprised of the chiral bipyrrolidine core and two bipyridine peripheral arms is introduced. Ligand 1 was found to bind in a fully diastereoselective and uniform mode around ZnII, FeII and CdII giving coordinatively inert octahedral "chiral-at-metal" complexes with the Δ4Λ2/Λ4Δ2 wrapping mode. Equimolar mixtures of quasienantiomeric pairs of these complexes exhibited a clear tendency to pack as quasiracemates as was revealed from the crystallographic structures of [(R,R)-1-Zn](PF6)2/[(S,S)-1-Fe](PF6)2 and [(R,R)-1-Zn](PF6)2/[(S,S)-1-Cd](PF6)2, in an isomorphous fashion to that of the racemic compound [rac-1-Zn](PF6)2 in space group C2/c.

AB - Aiming at a general methodology for binary co-assembly of complexes of different metals through quasiracemate crystallization, the hexadentate ligand 1 comprised of the chiral bipyrrolidine core and two bipyridine peripheral arms is introduced. Ligand 1 was found to bind in a fully diastereoselective and uniform mode around ZnII, FeII and CdII giving coordinatively inert octahedral "chiral-at-metal" complexes with the Δ4Λ2/Λ4Δ2 wrapping mode. Equimolar mixtures of quasienantiomeric pairs of these complexes exhibited a clear tendency to pack as quasiracemates as was revealed from the crystallographic structures of [(R,R)-1-Zn](PF6)2/[(S,S)-1-Fe](PF6)2 and [(R,R)-1-Zn](PF6)2/[(S,S)-1-Cd](PF6)2, in an isomorphous fashion to that of the racemic compound [rac-1-Zn](PF6)2 in space group C2/c.

KW - binary materials

KW - bipyrrolidine

KW - chiral ligands

KW - hexadentate ligands

KW - quasiracemate

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ER -

Assembling Quasi-enantiomeric Octahedral Complexes of Different Metals via Quasi-racemate Crystallization

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