Dataset Information

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes.

ABSTRACT: The use of antimony and bismuth in supramolecular chemistry has been largely overlooked in comparison to the lighter elements of Group 15, and the coordination chemistry of the tripodal ligands [Sb(3-py)₃] and [Bi(3-py)₃] (L) containing the heaviest p-block element bridgehead atoms has been unexplored. We show that these ligands form a common hybrid metal-organic framework (MOF) structure with Cu(I) and Ag(I) (M) salts of weakly coordinating anions (PF₆^-, SbF₆^-, and OTf^-), composed of a cationic substructure of rhombic cage (M)₄(L)₄ units linked by Sb/Bi-M bonding. The greater Lewis acidity of Bi compared to Sb can, however, allows anion···Bi interactions to overcome Bi-metal bonding in the case of BF₄^-, leading to collapse of the MOF structure (which is also seen where harder metals like Li⁺ are employed). This study therefore provides insight into the way in which the electronic effects of the bridgehead atom in these ligand systems can impact their supramolecular chemistry.

SUBMITTER: Garcia-Romero A

PROVIDER: S-EPMC8693195 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes.

García-Romero Álvaro Á Martín-Álvarez Jose M JM Miguel Daniel D Wright Dominic S DS Álvarez Celedonio M CM García-Rodríguez Raúl R

Inorganic chemistry 20211209 24

The use of antimony and bismuth in supramolecular chemistry has been largely overlooked in comparison to the lighter elements of Group 15, and the coordination chemistry of the tripodal ligands [Sb(3-py)3] and [Bi(3-py)3] (L) containing the heaviest p-block element bridgehead atoms has been unexplored. We show that these ligands form a common hybrid metal-organic framework (MOF) structure with Cu(I) and Ag(I) (M) salts of weakly coordinating anions (PF6-</su ...[more]

PMID: 34882394

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Project description:Supramolecular hydrogels have emerged as a class of promising biomaterials for applications such as drug delivery and tissue engineering. Self-assembling peptides have been well studied for such applications, but low molecular weight (LMW) amino acid-derived gelators have attracted interest as low-cost alternatives with similar emergent properties. Fluorenylmethyloxycarbonyl-phenylalanine (Fmoc-Phe) is one such privileged motif often chosen due to its inherent self-assembly potential. Previously, we developed cationic Fmoc-Phe-DAP gelators that assemble into hydrogel networks in aqueous NaCl solutions of sufficient ionic strength. The chloride anions in these solutions screen the cationic charge of the gelators to enable self-assembly to occur. Herein, we report the effects of varying the anions of sodium salts on the gelation potential, nanoscale morphology, and hydrogel viscoelastic properties of Fmoc-Phe-DAP and two of its fluorinated derivatives, Fmoc-3F-Phe-DAP and Fmoc-F5-Phe-DAP. It was observed that both the anion identity and gelator structure had a significant impact on the self-assembly and gelation properties of these derivatives. Changing the anion identity resulted in significant polymorphism of the nanoscale morphology of the assembled states that was dependent on the chemical structure of the gelator. The emergent viscoelastic character of the hydrogel networks was also found to be reliant on the anion identity and gelator structure. These results demonstrate the complex interplay between the gelator and environment that have a profound and often unpredictable impact on both self-assembly properties and emergent viscoelasticity in supramolecular hydrogels formed by LMW compounds. This work also illustrates the current lack of understanding that limits the rational design of potential biomaterials that will be in contact with complex biological fluids and provides motivation for additional research to correlate the chemical structure of LMW gelators with the structure and emergent properties of the resulting supramolecular assemblies as a function of environment.

Dataset Information

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes.

Publications

Cation- and Anion-Mediated Supramolecular Assembly of Bismuth and Antimony Tris(3-pyridyl) Complexes.

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