TY - JOUR
T1 - Host–Guest Hydrogen Bonding Varies the Charge-State Behavior of Magnetic Sponges
AU - Zhang, Jun
AU - Kosaka, Wataru
AU - Kitagawa, Yasutaka
AU - Miyasaka, Hitoshi
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research (No. 16H02269, 18K19050, 18K05055, 18H05208) from MEXT, Japan, and on Innovative Areas (“p-System Figuration” Area 2601, No. 17H05137) from JSPS, Japan, and the E-IMR project. J.Z. is thankful for the JSPS KAKENHI (No. 17J02497). Y.K. acknowledges the Inter-University Cooperative Research Program of the IMR, Tohoku University (No. 17K0030 and 18K0048).
PY - 2019/5/27
Y1 - 2019/5/27
N2 - The electron-donor(D) and -acceptor(A)-assembled D2A-layer framework [{Ru2(m-FPhCO2)4}2TCNQ(OMe)2]⋅nDCE (1-nDCE; m-FPhCO2−=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 nDCE. 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-nDCE (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 Tc 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.
AB - The electron-donor(D) and -acceptor(A)-assembled D2A-layer framework [{Ru2(m-FPhCO2)4}2TCNQ(OMe)2]⋅nDCE (1-nDCE; m-FPhCO2−=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 nDCE. 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-nDCE (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 Tc 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.
KW - electron transfer
KW - host–guest interactions
KW - hydrogen bonding
KW - magnetic sponges
KW - theoretical calculations
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U2 - 10.1002/anie.201902301
DO - 10.1002/anie.201902301
M3 - Article
C2 - 30941849
AN - SCOPUS:85065188315
VL - 58
SP - 7351
EP - 7356
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 22
ER -