Self-assembly of thiolate-protected silver coordination polymers regulated by POMs

Two polyoxometalate (POM)-based thiolate-protected silver coordination polymers were obtained using different Lindquist-type POM precursors under the same conditions. [Ag10(StBu)6(CH3CN)8(Mo6O19)2·2CH3CN]n (abbreviated as Ag10-Mo6) was observed to feature chain-like structures containing Ag10 clusters linked by [Mo6O19]2- anions through Ag-O bonds and to exhibit unprecedented green photoluminescence at room temperature. Interestingly, [Ag18(StBu)12(CH3CN)5(Mo6O19)2·Mo6O19·2CH3CN]n (abbreviated as Ag18-Mo6) was found to contain 20-membered cycle-Ag10S10 each with a diameter of approximately 11.382 Å and constructed from alternating silver and sulfur atoms and interconnected into an elegant Ag-S sheet by interstitial the Ag3StBu and AgCH3CN motifs, and to also contain [Mo6O19]2- counter ions filling in the spaces made by the cycle-Ag10S10 and strengthening the structure by forming Ag-O bonds. Such a stacking structure for thiolate-protected silver compounds has not been previously reported.