TY - JOUR
T1 - Slow Magnetic Relaxation Triggered by a Structural Phase Transition in Long-Chain-Alkylated Cobalt(II) Single-Ion Magnets
AU - Kobayashi, Fumiya
AU - Ohtani, Ryo
AU - Nakamura, Masaaki
AU - Lindoy, Leonard F.
AU - Hayami, Shinya
N1 - Funding Information:
This work was supported by a KAKENHI Grant-in-Aid for Scientific Research (A) (JP17H01200) and also by a JSPS Grant-in-Aid for Young Scientists (B) (JP18K14245) as well as a JSPS Grant-in-Aid for Scientific Research on Innovative Areas (Mixed Anion JP17H05485). This work was partially supported by the Cooperative Research Program of the “Network Joint Research Centre for Materials and Devices”.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/6/3
Y1 - 2019/6/3
N2 - The behavior of single-ion magnets (SIMs) that reflects large distortions of their coordination environments caused by the packing of long alkyl chains for two Co(II) complexes of the type [Co(Cn-terpy)2](BF4)2 (Cn-terpy = 4′-alkoxy-2,2':6′,2″-terpyridine; n = 10 (1), 16 (2)) is reported. 1·2MeOH, which features a highly distorted octahedral high-spin Co(II) center, exhibits field-induced slow magnetic relaxation under an applied dc field of 1000 Oe. Further detailed analysis of the relaxation process indicated the prevalence of the Raman process at low temperature. Surprisingly, 2 shows a reverse spin transition (rST) and also exhibits remarkable field-induced SIM behavior, revealing the presence of magnetic anisotropy for this high-spin Co(II) species that is triggered by a structural phase transition. We present here the first examples of the coexistence of field-induced slow magnetic relaxation and rST associated with structural phase transitions involving long-alkyl-chain conformational changes from gauche to anti. These results indicate the prospect of inducing SIM properties in other distorted high-spin Co(II) species bearing long alkyl chains.
AB - The behavior of single-ion magnets (SIMs) that reflects large distortions of their coordination environments caused by the packing of long alkyl chains for two Co(II) complexes of the type [Co(Cn-terpy)2](BF4)2 (Cn-terpy = 4′-alkoxy-2,2':6′,2″-terpyridine; n = 10 (1), 16 (2)) is reported. 1·2MeOH, which features a highly distorted octahedral high-spin Co(II) center, exhibits field-induced slow magnetic relaxation under an applied dc field of 1000 Oe. Further detailed analysis of the relaxation process indicated the prevalence of the Raman process at low temperature. Surprisingly, 2 shows a reverse spin transition (rST) and also exhibits remarkable field-induced SIM behavior, revealing the presence of magnetic anisotropy for this high-spin Co(II) species that is triggered by a structural phase transition. We present here the first examples of the coexistence of field-induced slow magnetic relaxation and rST associated with structural phase transitions involving long-alkyl-chain conformational changes from gauche to anti. These results indicate the prospect of inducing SIM properties in other distorted high-spin Co(II) species bearing long alkyl chains.
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U2 - 10.1021/acs.inorgchem.9b00543
DO - 10.1021/acs.inorgchem.9b00543
M3 - Article
C2 - 31117627
AN - SCOPUS:85066783208
SN - 0020-1669
VL - 58
SP - 7409
EP - 7415
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 11
ER -