Structure and Piezoelectricity Due to B Site Cation Variation in ABn+Cln+2Hybrid Histammonium Chlorometallate Materials

Michael Wells, Jacob Hempel, Santosh Adhikari, Qingping Wang, Daniel Allen, Alison Costello, Chris Bowen, Sean Parkin, Christopher Sutton, Aron J. Huckaba

Research output: Contribution to journalArticlepeer-review

Abstract

To provide new insights for understanding the influence of B site cations on the structure in chlorometallate materials of the form ABn+Cln+2, we report novel organic-inorganic hybrid metallates (OIHMs) incorporating histammonium (HistNH3) dications and various transition-metal and main group B site cations. Single crystals of OIHMs with the basic formula (HistNH3Mn+Cln+2, M = Fe, Co, Ni, Cu, Zn, Cd, Hg, Sb, Sn, Pb, Bi) were grown and their structures characterized by single-crystal X-ray crystallography. HistNH3CoCl4, HistNH3ZnCl4, and HistNH3SbCl5were crystallized in a non-centrosymmetric space group and were subsequently studied with piezoresponse force microscopy (PFM). While bulk measurements of crystals and poly(vinylidene difluoride) (PVDF)/metallate composite films exhibited low bulk response values, the surface-measured local response values using PFM were 5.17 pm/V for HistNH3CoCl4, 22.6 pm/V for HistNH3ZnCl4, and 2.9 pm/V for HistNH3SbCl5compared with 2.50 pm/V for PVDF reference samples. The magnitudes of the d33coefficient, net dipole, and cation-Cl bond dipole obtained from the density functional theory calculations confirm the higher response in HistNH3ZnCl4compared to HistNH3CoCl4. Density of states and crystal orbital Hamilton population analysis indicate that the higher net dipole in HistNH3ZnCl4compared to HistNH3CoCl4is due to the lower hybridization of the M-Cl bond.

Original languageEnglish
Pages (from-to)17746-17758
Number of pages13
JournalInorganic Chemistry
Volume61
Issue number44
DOIs
StatePublished - Nov 7 2022

Bibliographical note

Funding Information:
We thank Prof. Y. T. Cheng for access to PFM instrumentation. C.S. and S.A. acknowledge support from the University of South Carolina and AFOSR (20IOE044). A.H. acknowledges startup funds from the University of Kentucky and D.A. acknowledges REU funding (NSF 1757354). This material is based upon work supported by the National Science Foundation under Cooperative agreement no. 1849213.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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