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Article Abstract
Three polymorphs of a semiconducting Cd(II)-thiolate coordination polymer with the formula [Cd(2-SNPh)] (2-HSNPh = 2-naphthalenethiol) have been reported. Single-crystal X-ray structural analysis revealed that adopts a one-dimensional (1D) structure composed of single-strand (-Cd-S-) ladder chains, whereas adopts a 1D architecture with double-strand (-Cd-S-) chains assembled through S···S interactions. In contrast, microcrystal electron diffraction analysis demonstrated that , obtained through thermal treatment of and , exhibits the formation of a 1D structure comprising triple-strand (-Cd-S-) chains, also formed via S···S interactions. This thermally induced, irreversible structural transformation to is accompanied by a transition from a nonpolar structure to a polar structure, leading to the emergence of second harmonic generation activity. Furthermore, time-resolved microwave conductivity measurements and first-principles calculations demonstrated that all three polymorphs exhibit photoconductivity, which is attributed to charge transport along the inorganic (-Cd-S-) chains via a hopping mechanism.
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