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Host–Guest Hydrogen Bonding Varies the Charge‐State Behavior of Magnetic Sponges
Author(s) -
Zhang Jun,
Kosaka Wataru,
Kitagawa Yasutaka,
Miyasaka Hitoshi
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201902301
Subject(s) - electron donor , electron acceptor , hydrogen bond , crystallography , chemistry , electron , charge (physics) , solvation , tetracyanoquinodimethane , acceptor , ferrimagnetism , chemical physics , solvent , materials science , condensed matter physics , photochemistry , molecule , organic chemistry , physics , magnetization , magnetic field , quantum mechanics , catalysis
The electron‐donor(D) and ‐acceptor(A)‐assembled D 2 A‐layer framework [{Ru 2 ( m ‐FPhCO 2 ) 4 } 2 TCNQ(OMe) 2 ]⋅ n DCE ( 1‐ n DCE ; m ‐FPhCO 2 − = m ‐fluorobenzoate; TCNQ(OMe) 2 =2,5‐dimethoxyl‐7,7,8,8‐tetracyanoquinodimethane; DCE=1,2‐dichloroethane) undergoes drastic charge‐ordered state variations via three distinct states that are a two‐electron‐transferred state (2e‐I), a charge‐disproportionated state (1.5e‐I), and a one‐electron‐transferred state (1e‐I), depending on the degree of solvation by n DCE. The pristine form 1‐4DCE has a paramagnetic 2e‐I state, which eventually produces the solvent‐free form 1 in 1.5e‐I via an intermediate state 1‐ n DCE ( n ≤1) in 1e‐I. Resolvation of 1 stabilizes 1‐DCE , allowing it to switch between 1.5e‐I and 1e‐I, and to become ferrimagnetic with a T c of 30 K (1.5e‐I) and 88 K (1e‐I). The stabilization of the 1e‐I state of 1‐DCE is due to the presence of host–guest hydrogen bonding that enables to suppress the electron‐donation ability of D even in an identical framework with 1 .