Issue 17, 2025

A new supramolecular tecton: the crucial impact of the polycation charge and geometry of H-bonds on the structure and properties of halometallates in the solid state

Abstract

A new tricationic organic supramolecular tecton has been designed and synthesized. Contrary to known mono- and dicationic species, this new molecule, being a “three-way connector”, allows assembling infinite supramolecular sheets and nets upon interaction with appropriate inorganic counterpart complex anions. In this work, triprotonated 6-amino-5,7-dimethyl-1,3-diazaadamantane, comprising two secondary and one primary nitrogen atoms, is used as a trication to form hybrid compounds with iodometallate anions by forming five hydrogen bonds at a time. It is shown that the bulky cation works simultaneously as a spacer and a connector, such that the positions of inorganic [MI6]3− anions (M = Sb or Bi) in the crystal structures are defined by five hydrogen bonds and are well-separated from each other. The latter is considered as a prerequisite for the hybrid compounds to exhibit optical properties originating from the undisturbed electronic structure of individual inorganic anions.

Graphical abstract: A new supramolecular tecton: the crucial impact of the polycation charge and geometry of H-bonds on the structure and properties of halometallates in the solid state

Supplementary files

Article information

Article type
Paper
Submitted
09 Feb 2025
Accepted
24 Mar 2025
First published
25 Mar 2025

Dalton Trans., 2025,54, 6983-6992

A new supramolecular tecton: the crucial impact of the polycation charge and geometry of H-bonds on the structure and properties of halometallates in the solid state

T. A. Shestimerova, A. V. Medved'ko, M. A. Bykov, M. A. Kalinin, M. T. Metlin, I. V. Taydakov, V. E. Gontcharenko, Z. Wei, E. V. Dikarev, S. Z. Vatsadze and A. V. Shevelkov, Dalton Trans., 2025, 54, 6983 DOI: 10.1039/D5DT00318K

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