TY - JOUR
T1 - Intermolecular Interaction Tuning of Spin-Crossover Iron(III) Complexes with Aromatic Counteranions
AU - Tsukiashi, Asami
AU - Nakaya, Manabu
AU - Kobayashi, Fumiya
AU - Ohtani, Ryo
AU - Nakamura, Masaaki
AU - Harrowfield, Jack M.
AU - Kim, Yang
AU - Hayami, Shinya
PY - 2018/3/5
Y1 - 2018/3/5
N2 - Iron(III) spin-crossover (SCO) complexes [Fe(qsal)2]BS·MeOH·H2O (1), [Fe(qsal)2](NS)·MeOH (2), [Fe(qnal)2](NS) (3), and [Fe(qnal)2]PS·MeOH·CH2Cl2 (4) (Hqsal, N-(8-quinolinyl)salicylaldimine; Hqnal, N-(8-quinolinyl)-2-hydroxy-1-naphthaldimine; BS, benzenesulfonate; NS, 1-naphthalenesulfonate; PS, 1-pyrenesulfonate) have been synthesized and characterized by X-ray structure determinations and temperature-dependent magnetic susceptibility measurements. The aromatic counteranions BS, NS, and PS can be used for the tuning of intermolecular coupling through a variety of weak interactions. All of the complexes show temperature-dependent SCO behavior. but the light-induced excited spin-state trapping (LIESST) effect was observed only for 1, 3, and 4 when the samples were illuminated (λ 808 nm) for 1 h at 5 K. In particular, 59% of the LS form of 1 was converted to the metastable HS state by illumination, equal to the highest degree of conversion yet known for LIESST in [Fe(qsal)2]+ derivatives. The lack of a LIESST effect for 2 may be due to the relatively limited degree of interaction between the cations and anions in the lattice, reflected in a much longer minimum Fe···Fe separation in this complex in comparison to the others.
AB - Iron(III) spin-crossover (SCO) complexes [Fe(qsal)2]BS·MeOH·H2O (1), [Fe(qsal)2](NS)·MeOH (2), [Fe(qnal)2](NS) (3), and [Fe(qnal)2]PS·MeOH·CH2Cl2 (4) (Hqsal, N-(8-quinolinyl)salicylaldimine; Hqnal, N-(8-quinolinyl)-2-hydroxy-1-naphthaldimine; BS, benzenesulfonate; NS, 1-naphthalenesulfonate; PS, 1-pyrenesulfonate) have been synthesized and characterized by X-ray structure determinations and temperature-dependent magnetic susceptibility measurements. The aromatic counteranions BS, NS, and PS can be used for the tuning of intermolecular coupling through a variety of weak interactions. All of the complexes show temperature-dependent SCO behavior. but the light-induced excited spin-state trapping (LIESST) effect was observed only for 1, 3, and 4 when the samples were illuminated (λ 808 nm) for 1 h at 5 K. In particular, 59% of the LS form of 1 was converted to the metastable HS state by illumination, equal to the highest degree of conversion yet known for LIESST in [Fe(qsal)2]+ derivatives. The lack of a LIESST effect for 2 may be due to the relatively limited degree of interaction between the cations and anions in the lattice, reflected in a much longer minimum Fe···Fe separation in this complex in comparison to the others.
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U2 - 10.1021/acs.inorgchem.7b03126
DO - 10.1021/acs.inorgchem.7b03126
M3 - Article
C2 - 29461818
AN - SCOPUS:85042938707
VL - 57
SP - 2834
EP - 2842
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 5
ER -