Magnetic Behaviors and Nonlinear Optical Properties of Heteroleptic Bis(phthalocyaninato) Holmium Compounds

Abstract Incorporating unsubstituted phthalocyanine and dibutylamino‐substituted phthalocyanine into sandwich‐type rare earth compounds has provided a heteroleptic bis(phthalocyaninato) trivalent holmium analogue. The rich redox states of sandwich‐type tetrapyrole‐based metal compounds lead to the formation of [(Pc)Ho{Pc{N(C 4 H 9 ) 2 } 8 }] . ( 1 ) and [(Pc)Ho{Pc[N(C 4 H 9 ) 2 ] 8 }] − ⋅ [(C 4 H 9 ) 4 N] + ( 2 ) as a neutral unprotonated and reduced state, respectively. The detailed sandwich‐type structures of these two homologs with different redox states are disclosed using single crystal X‐ray diffraction analyses. In addition, the differences in these two compounds with/without one radical have been ascertained by fundamental spectroscopic instruments, enabling the adjustment of the corresponding static magnetic behaviors and nonlinear optical properties owing to the presence/absence of radical‐Ho(III) interaction and different electron cloud density delocalized around 1 and 2 .