Hybrid Layered Double Perovskite Halides of Transition Metals

Pratap Vishnoi; Julia L Zuo; Xiaotong Li; Devesh Chandra Binwal; Kira E Wyckoff; Lingling Mao; Linus Kautzsch; Guang Wu; Stephen D Wilson; Mercouri G Kanatzidis; Ram Seshadri; Anthony K Cheetham

doi:10.1021/jacs.1c12760

Hybrid Layered Double Perovskite Halides of Transition Metals

J Am Chem Soc. 2022 Apr 20;144(15):6661-6666. doi: 10.1021/jacs.1c12760. Epub 2022 Apr 4.

Authors

Pratap Vishnoi^{1

2}, Julia L Zuo¹, Xiaotong Li³, Devesh Chandra Binwal², Kira E Wyckoff¹, Lingling Mao^{1

4}, Linus Kautzsch¹, Guang Wu⁵, Stephen D Wilson¹, Mercouri G Kanatzidis³, Ram Seshadri¹, Anthony K Cheetham^{1

6}

Affiliations

¹ Materials Department and Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States.
² New Chemistry Unit and International Centre for Materials Science, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore 560064, India.
³ Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
⁴ Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, 518055 China.
⁵ Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
⁶ Department of Materials Science & Engineering, National University of Singapore, 117576, Singapore, Singapore.

PMID: 35377623
DOI: 10.1021/jacs.1c12760

Abstract

Hybrid layered double perovskite (HLDP) halides comprise hexacoordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with Pb^II (such as Sb^III and Bi^III). Here, we report eight HLDP halides from the A₂M^IM^IIIX₈ family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA), or 1,3-propanediammonium (1,3-PDA); M^I = Cu or Ag; M^III = Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)₂Ag^IRu^IIICl₈ and (PPDA)₂Ag^IMo^IIICl₈ show no obvious evidence of a magnetic ordering transition. While the t_2g³ Mo^III compound displays Curie-Weiss behavior for a spin-only d³ ion, the t_2g⁵ Ru^III compound displays marked deviations from the Kotani theory.