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((SBu)-Bu-t)(6)(CH3CN)(8)(Mo6O19)(2)center dot 2CH(3)CN](n)(abbreviated asAg(10)-Mo-6) was observed to feature chain-like structures containing Ag(10)clusters linked by [Mo6O19](2-)anions through Ag-O bonds and to exhibit unprecedented green photoluminescence at room temperature. Interestingly, [Ag-18((SBu)-Bu-t)(12)(CH3CN)(5)(Mo6O19)(2)center dot Mo6O19 center dot 2CH(3)CN](n)(abbreviated asAg(18)-Mo-6) was found to contain 20-membered cycle-Ag(10)S(10)each with a diameter of approximately 11.382 angstrom and constructed from alternating silver and sulfur atoms and interconnected into an elegant Ag-S sheet by interstitial the (Ag3SBu)-Bu-t and AgCH3CN motifs, and to also contain [Mo6O19](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.