Silver Thiolate Nano‐sized Molecular Clusters and Their Supramolecular Covalent Frameworks: An Approach Toward Pre‐templated Synthesis. Issue 20 (26th September 2017)

• Record Type: Journal Article
• Authors: Chen, Zi‐Yi; Tam, Dennis Y. S.; Zhang, Leon Li‐Min; Mak, Thomas C. W.
• Is Part Of: Chemistry, an Asian journal. Volume 12:Issue 20(2017)
• Page Start: 2763
• Page End: 2769
• Publication Date: 2017-09-26
• Subjects: cluster compounds -- metal-organic frameworks -- silver thiolate -- supramolecular chemistry -- X-ray crystallography; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201701150
• Languages: English
• ISSNs: 1861-4728

Abstract

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 Ag2 C2 using a C2 2− pre‐templated approach. Herein, two prototype clusters Ag14 (SR)6 and CO3 @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, Ag14 (S‐ i Pr)6 (CO2 CF3 )8 ⋅(DMSO)6 (two polymorphic forms1, 2 ) and [Ag14 (S‐Cy)6 (CO2 CF3 )8 (DMSO)4 ]⋅(DMSO)3 (3 ), and a cluster‐based metal–organic framework {Ag3 [Ag14 (S‐ i Pr)6 (CO2 CF3 )11 (H2 O)3 CH3 OH]⋅(H2 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(CH3 )2 CO]⋅[CO3 @Ag18 (S‐ t Bu)10 (NO3 )7 (DMF)4 ]⋅DMF} n (5 ), as well as two layer‐type compounds, namely, {Ag[CO3 @Ag20 (S‐ i Pr)10 (CO2 CF3 )9 (CO2 HCF3 )(CH3 OH)2 ]} n (6 ) and {Ag2 [CO3 @Ag20 (S‐Cy)10 (CO2 CF3 )10 (CO2 HCF3 )2 (H2 O)2 ]⋅(H2 O)3 ⋅(CH3 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 C2 @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. Abstract : From nanocluster to covalent framework : Silver‐thiolate molecular clusters and their supramolecular covalent frameworks have been assembled from the silver carbide precursor Ag2 C2 using a C2 2− pre‐templated approach.