4.7 Article

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

Journal

DALTON TRANSACTIONS
Volume 51, Issue 30, Pages 11547-11557

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2dt01292h

Keywords

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Funding

  1. Center for Synthetic Control Across Length Scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0019381]
  2. UC Santa Barbara Materials Research Science and Engineering Center (MRSEC) [NSF DMR 1720256]

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This work discusses the synthesis and characterization of a 2D coordination polymer composed of a dianionic perhydroxylated boron cluster coordinated to Zn(ii). Rigorous characterization techniques revealed the structure of the material and showed evidence of the dianionic boron cluster adjusting its coordination to Zn(ii) in the solid state.
In this work, we discuss the synthesis and characterization of a 2D coordination polymer composed of a dianionic perhydroxylated boron cluster, [B-12(OH)(12)(2-)], coordinated to Zn(ii)-the first example of a transition metal-coordinated [B-12(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 B-11 and H-1 nuclei, suggesting the full removal of coordinated solvent molecules. Evidence also suggested that [B-12(OH)(12)(2-)] can adjust its coordination to Zn(ii) in the solid-state through hemilability of its numerous -OH ligands.

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