Chiral effects at the metal center in Fe(III) spin crossover coordination salts

Mohammad Zaz; Wai Kiat Chin; Gauthami Viswan; Arjun Subedi; Esha Mishra; Kayleigh McElveen; Binny Tamang; David Shapiro; Alpha T N'Diaye; Rebecca Y Lai; Peter A Dowben

doi:10.1088/1361-648X/ada338

Chiral effects at the metal center in Fe(III) spin crossover coordination salts

J Phys Condens Matter. 2024 Dec 24. doi: 10.1088/1361-648X/ada338. Online ahead of print.

Authors

Mohammad Zaz¹, Wai Kiat Chin², Gauthami Viswan³, Arjun Subedi⁴, Esha Mishra⁵, Kayleigh McElveen⁶, Binny Tamang⁷, David Shapiro⁸, Alpha T N'Diaye⁹, Rebecca Y Lai¹⁰, Peter A Dowben¹¹

Affiliations

¹ Physics and Astronomy, University of Nebraska-Lincoln, 855 N 16th street, Lincoln, Nebraska, 68588-0299, UNITED STATES.
² physics and astronomy, University of Nebraska-Lincoln, Theodore Jorgensen Hall, 855 N16th street, Lincoln, Nebraska, 68588-0299, UNITED STATES.
³ Physics and Astronomy, University of Nebraska-Lincoln, Theodore Jorgensen Hall, N 16 th Street, Lincoln, Nebraska, 68588-0299, UNITED STATES.
⁴ Physics and Astronomy, University of Nebraska-Lincoln, 855 N 16th Street, Lincoln, Nebraska, 68588-0299, UNITED STATES.
⁵ Department of Physics and Astronomy, University of Nebraska-Lincoln, 855 N 16th Street, Lincoln, Nebraska, 68588-0299, UNITED STATES.
⁶ Department of Chemistry, University of Nebraska-Lincoln, Hamilton hall, Lincoln, Nebraska, 68588-0304, UNITED STATES.
⁷ Department of Chemistry, University of Nebraska-Lincoln, Hamilton Hall, Lincoln, Nebraska, 68588-0304, UNITED STATES.
⁸ Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Mailstop15R342, Berkeley, Berkeley, California, 94720-8099, UNITED STATES.
⁹ Advanced Light Source, Lawrence Berkeley National Laboratory, One Cyclotron Road, MS 72-150, Berkeley, CA 94720-8250, USA, Berkeley, California, 94720-8099, UNITED STATES.
¹⁰ Chemistry, University of Nebraska-Lincoln, 651 Hamilton Hall, Lincoln, Nebraska, 68588-0304, UNITED STATES.
¹¹ Department of Physics and Astronomy, University of Nebraska-Lincoln, Jorgenesen Hall, 855 North 16th Street, Lincoln, Nebraska, 68588-0299, UNITED STATES.

PMID: 39719127
DOI: 10.1088/1361-648X/ada338

Abstract

Evidence of chirality was observed at the Fe metal center in Fe(III) spin crossover coordination salts [Fe(qsal)₂Ni(dmit)₂] and [Fe(qsal)₂(TCNQ)₂] from X-ray absorption spectroscopy at the Fe 2p_3/2core threshold. Based on the circularly polarized X-ray absorption data, the X-ray natural circular dichroism seen [Fe(qsal)₂Ni(dmit)₂] and [Fe(qsal)₂(TCNQ)₂] is far stronger than seen for [Fe(qsal)₂Cl] suggesting this natural circular dichroism signature is a ligand effect rather than a result of just a loss of octahedral symmetry on the Fe core. The larger the chiral effects in the Fe 2p core to bound X-ray absorption, the greater the perturbation of the Fe 2p_3/2to 2p_1/2spin-orbit splitting seen in the X-ray absorption spectra.&#xD.

Keywords: Chirality; Dichroism; Spin crossover.

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