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Title: Hydrogen Bonding Controls the Structural Evolution in Perovskite-Related Hybrid Platinum(IV) Iodides

Abstract

In this paper, we describe the solid-state structural evolution in four hybrid hexaiodoplatinate(IV) compounds, demonstrating the increasingly important role that extended hydrogen bonding plays in directing the structure across the series. The compounds are A 2PtI 6, where A is one of the following amines: ammonium, NH 4 +; methylammonium, CH 3NH 3 +; formamidinium, CH(NH 2) 2 +; guanidinium, C(NH 2) 3 +. These are closely related in structure and properties to the hybrid halide perovskites of lead(II) that have recently established their prowess in optoelectronics. The first three of these compounds crystallize in the vacancy-ordered double perovskite A 2Pt$$\square$$I 6 ($$\square$$ indicates a vacant site) structure in the K 2PtCl 6 archetype, despite the relatively large perovskite tolerance factors involved. The last compound, (GUA) 2PtI 6, crystallizes in a vacancy-ordered variant of the hexagonal CsNiCl 3 structure: the K 2MnF 6 structure. A combination of solid-state 195Pt and 1H NMR spectroscopy and detailed density functional theory calculations helps to reveal structural trends and establish the hydrogen-bonding tendencies. Finally, the calculations and measured optical properties support the surprising observation in these iodosalt compounds that, for smaller A cations, the conduction bands are considerably disperse, despite lacking extended I–Pt–I connectivity.

Authors:
 [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Univ. of California, Santa Barbara, CA (United States); National Univ. of Singapore (Singapore)
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1599740
Grant/Contract Number:  
SC0012541; DMR-1720256; CNS-1725797; DGE-1144085
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 16; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Evans, Hayden A., Fabini, Douglas H., Andrews, Jessica L., Koerner, Mitchell, Preefer, Molleigh B., Wu, Guang, Wudl, Fred, Cheetham, Anthony K., and Seshadri, Ram. Hydrogen Bonding Controls the Structural Evolution in Perovskite-Related Hybrid Platinum(IV) Iodides. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b01597.
Evans, Hayden A., Fabini, Douglas H., Andrews, Jessica L., Koerner, Mitchell, Preefer, Molleigh B., Wu, Guang, Wudl, Fred, Cheetham, Anthony K., & Seshadri, Ram. Hydrogen Bonding Controls the Structural Evolution in Perovskite-Related Hybrid Platinum(IV) Iodides. United States. doi:10.1021/acs.inorgchem.8b01597.
Evans, Hayden A., Fabini, Douglas H., Andrews, Jessica L., Koerner, Mitchell, Preefer, Molleigh B., Wu, Guang, Wudl, Fred, Cheetham, Anthony K., and Seshadri, Ram. Fri . "Hydrogen Bonding Controls the Structural Evolution in Perovskite-Related Hybrid Platinum(IV) Iodides". United States. doi:10.1021/acs.inorgchem.8b01597. https://www.osti.gov/servlets/purl/1599740.
@article{osti_1599740,
title = {Hydrogen Bonding Controls the Structural Evolution in Perovskite-Related Hybrid Platinum(IV) Iodides},
author = {Evans, Hayden A. and Fabini, Douglas H. and Andrews, Jessica L. and Koerner, Mitchell and Preefer, Molleigh B. and Wu, Guang and Wudl, Fred and Cheetham, Anthony K. and Seshadri, Ram},
abstractNote = {In this paper, we describe the solid-state structural evolution in four hybrid hexaiodoplatinate(IV) compounds, demonstrating the increasingly important role that extended hydrogen bonding plays in directing the structure across the series. The compounds are A2PtI6, where A is one of the following amines: ammonium, NH4+; methylammonium, CH3NH3+; formamidinium, CH(NH2)2+; guanidinium, C(NH2)3+. These are closely related in structure and properties to the hybrid halide perovskites of lead(II) that have recently established their prowess in optoelectronics. The first three of these compounds crystallize in the vacancy-ordered double perovskite A2Pt$\square$I6 ($\square$ indicates a vacant site) structure in the K2PtCl6 archetype, despite the relatively large perovskite tolerance factors involved. The last compound, (GUA)2PtI6, crystallizes in a vacancy-ordered variant of the hexagonal CsNiCl3 structure: the K2MnF6 structure. A combination of solid-state 195Pt and 1H NMR spectroscopy and detailed density functional theory calculations helps to reveal structural trends and establish the hydrogen-bonding tendencies. Finally, the calculations and measured optical properties support the surprising observation in these iodosalt compounds that, for smaller A cations, the conduction bands are considerably disperse, despite lacking extended I–Pt–I connectivity.},
doi = {10.1021/acs.inorgchem.8b01597},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 16,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

The capricious nature of iodine catenation in I 2 excess, perovskite-derived hybrid Pt( iv ) compounds
journal, January 2019

  • Evans, Hayden A.; Andrews, Jessica L.; Fabini, Douglas H.
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Polymorphism in M(H 2 PO 2 ) 3 (M = V, Al, Ga) compounds with the perovskite-related ReO 3 structure
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  • Evans, Hayden A.; Deng, Zeyu; Collings, Ines E.
  • Chemical Communications, Vol. 55, Issue 20
  • DOI: 10.1039/c9cc00118b

Perovskites with d-block metals for solar energy applications
journal, January 2019

  • Theofylaktos, Lazaros; Kosmatos, Kyro Odysseas; Giannakaki, Eleni
  • Dalton Transactions, Vol. 48, Issue 26
  • DOI: 10.1039/c9dt01485c

Structural Diversity and Magnetic Properties of Hybrid Ruthenium Halide Perovskites and Related Compounds
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  • Vishnoi, Pratap; Zuo, Julia L.; Strom, T. Amanda
  • Angewandte Chemie International Edition, Vol. 59, Issue 23
  • DOI: 10.1002/anie.202003095