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Updated: Apr 27, 2026
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Anion templating from a silver(i) dithiophosphate 1D polymer forming discrete cationic and neutral octa- and
Jian-Hong Liao1, Hao-Wei Chang, Yi-Juan Li
1Department of Chemistry, National Dong Hwa University, Hualien, Taiwan 97401, Republic of China. chenwei@mail.ndhu.edu.tw.
Abstract:
We report on a Ag5 coordination polymer and discrete Ag8 and Ag10 dithiophosphate clusters. The cluster formation and structures were affected by the stoichiometric control of the M : L molar ratios used. The cluster [Ag5{S2P(O(i)Pr)2}4]n(PF6)n, , is a monomeric unit within a coordination polymer formed through the reaction between [Ag(CH3CN)4]PF6 and the dithiophosphate ligand, [S2P(O(i)Pr)2](-), used in a M : L molar ratio of 5 : 4. All other clusters formed in the study are discrete units with encapsulated anions within the metal framework. The clusters [Ag8(X){S2P(O(i)Pr)2}6](PF6) (X = F, , Cl, , Br, ) are all cationic and contain monoanionic halogens. The related cluster [Ag8(H/D){S2P(O(i)Pr)2}6](PF6) contains either a hydride or a deuteride ion, and , respectively. The cluster [Ag8(S){S2P(O(i)Pr)2}6], , is neutral due to the di-anionic nature of the encapsulated sulfide anion. Clusters were all formed by reacting [Ag(CH3CN)4]PF6 and [S2P(O(i)Pr)2](-) in a M : L molar ratio of 8 : 6 and stirring for 1 h in THF; thereafter the respective anions (one equiv.) were added in situ. The cluster [Ag10(I)4{S2P(O(i)Pr)2}6], , is also neutral due to the charge balancing of the additional metal and halogen. In this case the M : L : X molar ratio was 10 : 6 : 4. All new clusters were characterized by (1)H and (31)P NMR, and elemental analysis, and , , were characterized by single crystal X-ray diffraction.
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