Glycine‐Induced Unique Crystal Packing of Octacyanidetungstates With Strong Intermolecular Antiferromagnetic Interaction, Near‐Infrared Emission, and Second Harmonic Generation
Abstract
ABSTRACT We report a supramolecular assembly of octacyanidetungstates ( S = 1/2) with glycine, Cs 3 [W V (CN) 8 ](glycine), featuring a one‐dimensional columnar structure with a remarkably strong intermolecular antiferromagnetic superexchange interaction of J = −42.41(2) K between adjacent octacyanidetungstates due to their effective packing close to van der Waals contacts. This represents the strongest intermolecular spin‐spin interaction reported to date among cyanidemetallates. When exposed to 470 nm light, this compound exhibits a near‐infrared emission with a peak at 763 nm originating from the ligand‐to‐metal charge‐transfer excited state of [W V (CN) 8 ] 3− . Such emission is notably rare for d 1 metal complexes. Additionally, the noncentrosymmetric crystal structure of this compound enables second harmonic generation, emitting second harmonic light at 650 nm when irradiated with 1300 nm incident light.
Article Details
Authors (9)
Tatsuya Konishi
Department of Chemistry School of Science The University of Tokyo Tokyo Japan
Koji Nakabayashi
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Kunal Kumar
Takeshi Suzuki
Department of Virology, Graduate School of Medicine, Nagoya University
Kozo Okazaki
Institute for Solid State Physics, The University of Tokyo
Masataka Kobayashi
Institute for Solid State Physics The University of Tokyo Kashiwa Chiba Japan
Hidefumi Akiyama
Institute for Solid State Physics The University of Tokyo Kashiwa Chiba Japan
Kouji Chiba
Material Science Div. MOLSIS Inc. Chuo‐ku Tokyo Japan
Shin‐ichi Ohkoshi
Department of Chemistry School of Science The University of Tokyo Tokyo Japan