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Updated: May 23, 2025
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Chirality and Polarity Modulation in Semiconductive Zinc(II) Coordination Polymers Containing Thiolate-Based Ligands
Shion Tsujimura1, Ryohei Akiyoshi1, Akinori Saeki2
1School of Science, Kwansei Gakuin University, 1 Gakuen Uegahara, Sanda, Hyogo 669-1330, Japan.
Abstract:
Recently, chiral semiconductors have attracted considerable attention owing to their potential applicability in optoelectronics and spintronics. In this study, homochiral and heterochiral semiconductive Zn(II) coordination polymers [Zn(tbbt)((X)-mba)2]·solvent (H2tbbt = 4,4'-thiobisbenzenethiol, mba = methylbenzylamine, X = R, S, rac) were systematically synthesized. Single-crystal X-ray diffraction analyses revealed that KGF-57() and KGF-57() (KGF = Kwansei Gakuin framework), of type [Zn(tbbt)((X)-mba)2]·(X)-mba, obtained from enantiopure (R)-mba and (S)-mba isomers, exhibited chiral-nonpolar homochiral one-dimensional (1D) structures with mba lattice solvents, comprising left- and right-handed helical chains, respectively. Conversely, when using (rac)-mba, two heterochiral 1D architectures were obtained depending on synthetic temperature and solvent. Specifically, KGF-57() of type [Zn(tbbt)((rac)-mba)2]·(rac)-mba·nH2O exhibited an achiral-nonpolar heterochiral 1D structure with (rac)-mba and H2O lattice solvents, containing alternately aligned left-handed helical chains with (R)-mba and right-handed helical chains with (S)-mba. Conversely, KGF-58() with the formula [Zn(tbbt)((rac)-mba)2] formed an achiral-polar assembly without mba lattice solvents. This structure is composed of zigzag chains with either (R)-mba or (S)-mba in a heterochiral arrangement. Time-resolved microwave conductivity measurements and first-principles calculations revealed that a series of Zn(II) coordination polymers exhibited photoconductivity originating from the Zn-thiolate-based skeleton. Furthermore, by exchanging the mba ligands coordinated to 1D Zn-thiolate chains, a reversible structural conversion accompanied by chirality and polarity variation was achieved.
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