Slow Magnetic Relaxation Triggered by a Structural Phase Transition in Long-Chain-Alkylated Cobalt(II) Single-Ion Magnets

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, 2shows 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.