Issue 30, 2022

Synthesis and structural properties of a 2D Zn(ii) dodecahydroxy-closo-dodecaborate coordination polymer

Abstract

In this work, we discuss the synthesis and characterization of a 2D coordination polymer composed of a dianionic perhydroxylated boron cluster, [B12(OH)122−], coordinated to Zn(II)—the first example of a transition metal-coordinated [B12(OH)12]2− compound. This material was synthesized via cation exchange from the starting cesium salt and then subjected to rigorous characterization prior to and after thermal activation. Numerous techniques, including XRD, FTIR, SEM, TGA, and solid-state NMR revealed a 2D coordination polymer composed of sheets of Zn(II) ions intercalated between planes of boron clusters. The as-synthesized material was then evacuated of solvent via thermal treatment, and atomic-level changes from this transformation were elucidated through a combination of 1D and 2D solid-state NMR analyses of 11B and 1H nuclei, suggesting the full removal of coordinated solvent molecules. Evidence also suggested that [B12(OH)122−] can adjust its coordination to Zn(II) in the solid-state through hemilability of its numerous –OH ligands.

Graphical abstract: Synthesis and structural properties of a 2D Zn(ii) dodecahydroxy-closo-dodecaborate coordination polymer

Supplementary files

Article information

Article type
Paper
Submitted
25 Apr 2022
Accepted
20 Jun 2022
First published
22 Jun 2022

Dalton Trans., 2022,51, 11547-11557

Author version available

Synthesis and structural properties of a 2D Zn(II) dodecahydroxy-closo-dodecaborate coordination polymer

A. D. Ready, S. M. Becwar, D. Jung, A. Kallistova, E. Schueller, K. P. Anderson, R. Kubena, R. Seshadri, B. F. Chmelka and A. M. Spokoyny, Dalton Trans., 2022, 51, 11547 DOI: 10.1039/D2DT01292H

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