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. [Ag 10 (S t Bu) 6 (CH 3 CN) 8 (Mo 6 O 19 ) 2 ·2CH 3 CN] n (abbreviated as Ag 10 -Mo 6 ) was observed to feature chain-like structures containing Ag 10 clusters linked by [Mo 6 O 19 ] 2− anions through Ag-O bonds and to exhibit unprecedented green photoluminescence at room temperature. Interestingly, [Ag 18 (S t Bu) 12 (CH 3 CN) 5 (Mo 6 O 19 ) 2 ·Mo 6 O 19 ·2CH 3 CN] n (abbreviated as Ag 18 -Mo 6 ) was found to contain 20-membered cycle-Ag 10 S 10 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 Ag 3 S t Bu and AgCH 3 CN motifs, and to also contain [Mo 6 O 19 ] 2− counter ions filling in the spaces made by the cycle-Ag 10 S 10 and strengthening the structure by forming Ag-O bonds. Such a stacking structure for thiolate-protected silver compounds has not been previously reported. The thiolate-protected silver coordination polymers connected by Lindquist-type POM shows good stability. The chain-like Ag 10 -Mo 6 exhibits green photoluminescence. Two-dimensional Ag 18 -Mo 6 was observed to contain a unique 20-membered cycle-Ag 10 S 10 .