Silver Thiolate Nano‐sized Molecular Clusters and Their Supramolecular Covalent Frameworks: An Approach Toward Pre‐templated Synthesis

Abstract A series of seven new complexes including silver‐thiolate molecular clusters and their covalent supramolecular frameworks have been assembled from the silver carbide precursor Ag 2 C 2 using a C 2 2− pre‐templated approach. Herein, two prototype clusters Ag 14 (SR) 6 and CO 3 @Ag m (SR) 10 (R=isopropyl, cyclohexyl or tert ‐butyl; m= 18 or 20) are employed to construct cluster‐based metal–organic frameworks of different dimensions. In particular, both new ellipsoidal tetradecanuclear molecular cluster compounds, namely, Ag 14 (S‐ i Pr) 6 (CO 2 CF 3 ) 8 ⋅(DMSO) 6 (two polymorphic forms 1 , 2 ) and [Ag 14 (S‐Cy) 6 (CO 2 CF 3 ) 8 (DMSO) 4 ]⋅(DMSO) 3 ( 3 ), and a cluster‐based metal–organic framework {Ag 3 [Ag 14 (S‐ i Pr) 6 (CO 2 CF 3 ) 11 (H 2 O) 3 CH 3 OH]⋅(H 2 O) 2.5 } n ( 4 ) have been isolated and structurally characterized. Furthermore, increased acidity of the reaction mixture afforded three carboxylate‐templated cluster based frameworks: a chain‐like compound {[HN(CH 3 ) 2 CO]⋅[CO 3 @Ag 18 (S‐ t Bu) 10 (NO 3 ) 7 (DMF) 4 ]⋅DMF} n ( 5 ), as well as two layer‐type compounds, namely, {Ag[CO 3 @Ag 20 (S‐ i Pr) 10 (CO 2 CF 3 ) 9 (CO 2 HCF 3 )(CH 3 OH) 2 ]} n ( 6 ) and {Ag 2 [CO 3 @Ag 20 (S‐Cy) 10 (CO 2 CF 3 ) 10 (CO 2 HCF 3 ) 2 (H 2 O) 2 ]⋅(H 2 O) 3 ⋅(CH 3 OH) 3 } n ( 7 ) exhibiting sql ‐net characteristics. It is demonstrated that the C≡C 2− pre‐template, which draws several Ag + ions together to form the C 2 @Ag n entity, plays an indispensable role in the syntheses of these compounds. Furthermore, covalent linkage of these nano‐sized silver thiolate clusters from one‐ to three‐dimensions revealed enormous potential for the future development of silver cluster‐based frameworks.