Sulfur-coordinated coordination polymers (S-CPs) have unique optoelectrical properties that originate from infinite M-S bond networks. In this study, we synthesized and characterized two polymorphs of a two-dimensional Pb(II) S-CP with a formula of [Pb(tzdt)(OAc)] (Htzdt = 1,3-thiazolidine-2-thione, OAc = acetate). Our findings revealed that the thermodynamic product (KGF-26) possesses (-Pb-O-)n chains only, whereas the kinetic product (KGF-27) has both one-dimensional (-Pb-O-)n chains and two-dimensional (-Pb-S-)n layers. The results of time-resolved microwave conductivity measurements and first-principles calculations confirmed that KGF-27 exhibits higher photoconductivity than KGF-26, which establishes that the inorganic (-Pb-S-)n networks formed in S-CPs are crucial for achieving high photoconductivity. This is the first experimental demonstration of the impact of the (-M-S-)n networks in S-CPs on photoconductivity through the comparison of crystal polymorphisms.
Keywords: Polymorphism; coordination polymers; crystal stracture; photo-conductivity; semiconductor.
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