Two enantiomerically pure 9,9'-spirobifluorene-based bis(pyridine) ligands 1 and 2 were prepared to study their self-assembly behavior upon coordination to cis-protected palladium(II) ions. Whereas the sterically more demanding ligand, 2, gave rise to the expected dinuclear metallosupramolecular M2L2 rhombi, the sterically less demanding ligand, 1, acts as a template to give rise to a homochiral metallosupramolecular M4L4 catenane.
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http://dx.doi.org/10.1002/chem.201403414 | DOI Listing |
Dalton Trans
October 2023
School of Chemistry and Molecular Biosciences, The University of Queensland, St Lucia, Qld, 4072, Australia.
Despite the use of achiral ligands, the vast majority of metallosupramolecular assemblies containing octahedral tris-bidentate metal centres show strong stereochemical communication between metal centres, generally resulting in homochiral assemblies even though they are statistically disfavoured. Here we show that when resolved stereocentres are attached to the central part of a quaterpyridine ligand, the stereochemical coupling from this centre is insufficient to disrupt the strong stereochemical communication between metal centres in both [ML] helicates and [ML] tetrahedra.
View Article and Find Full Text PDFIUCrJ
May 2023
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Gyeonggi-do 15588, Republic of Korea.
Three novel hierarchical Ni-based metallosupramolecular cages were constructed from nickel ions, pyridine dicarboxylates and isophthalate derivative ligands (the substituents on C5 of isophthalate are methyl, tert-butyl and bromo groups). In every cage, two multinuclear nickel clusters, assembled from four nickel atoms and three pyridine dicarboxylate ligands, are interlinked by three isophthalate-derivative ligands to form a nickel-based triple-stranded helicate (TSH), which then becomes the supramolecular building block for the fabrication of a metallocage. Six homochiral TSH supramolecular building blocks, either left (M)-handed or right (P)-handed, are connected by four linking nickel atoms to generate M and P discrete racemic cage molecules (M - cage with six M-TSHs; P - cage with six P-TSHs).
View Article and Find Full Text PDFJ Am Chem Soc
January 2023
Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium.
Two-dimensional (2D) chirality has been actively studied in view of numerous applications of chiral surfaces such as in chiral resolutions and enantioselective catalysis. Here, we report on the expression and amplification of chirality in hybrid 2D metallosupramolecular networks formed by a nucleobase derivative. Self-assembly of a guanine derivative appended with a pyridyl node was studied at the solution-graphite interface in the presence and absence of coordinating metal ions.
View Article and Find Full Text PDFChirality
October 2021
Institute Physical and Chemistry Materials of Strasbourg, CNRS University of Strasbourg, Strasbourg, France.
We report on the polymerization/depolymerization of chiral metallo-supramolecular assembly by Cu /Cu redox change. By combining a monotopic enantiopure ligand with a ditopic ligand of opposite configuration, ML -type complexes are generated with chiral self-recognition or self-discrimination depending on the oxidation state of copper. In presence of Cu , the formation of heterochiral complexes is favored, thus generating dinuclear species whereas Cu advocates for the formation of homochiral species, namely, a mixture of mononuclear species and metallo-supramolecular polymeric species.
View Article and Find Full Text PDFChem Sci
March 2021
EaStCHEM School of Chemistry, The University of Edinburgh David Brewster Road Edinburgh EH93FJ UK
Reaction of Ni(OTf) with the bisbidentate quaterpyridine ligand results in the self-assembly of a tetrahedral, paramagnetic cage [Ni ]. By selectively exchanging the bound triflate from [OTf⊂Ni ](OTf) (), we have been able to prepare a series of host-guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MX⊂Ni ](OTf), where MX = MnCl (), CoCl (), CoBr (), NiCl (), and CuBr () or [MX⊂Ni ](OTf), where MX = FeCl () and FeBr (). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations.
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