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(C _n -terpy) ₂ ](BF ₄ ) ₂ (C _n -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.