General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters |
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| Authors: | Xiao‐Yu Li Dr Hai‐Feng Su Rui‐Qi Zhou Sheng Feng Prof Yuan‐Zhi Tan Dr Xing‐Po Wang Jiong Jia Prof Mohamedally Kurmoo Dr Di Sun Prof Lan‐Sun Zheng |
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| Institution: | 1. Key Lab for Colloid and Interface Chemistry of Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan, P.R. China;2. Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China;3. Institut de Chimie de Strasbourg, Université de Strasbourg, CNRS-UMR 7177, Strasbourg Cedex, France |
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| Abstract: | A general class of C3‐symmetric Ag9 clusters, Ag9S(tBuC6H4S)6(dpph)3(CF3SO3)] ( 1 ), Ag9(tBuC6H4S)6(dpph)3(CF3SO3)2] ? CF3SO3 ( 2 ), Ag9(tBuC6H4S)6(dpph)3(NO3)2] ? NO3 ( 3 ), and Ag9(tBuC6H4S)7(dpph)3(Mo2O7)0.5]2 ? 2 CF3COO ( 4 ) (dpph=1,6‐bis(diphenylphosphino)hexane), with a twisted trigonal‐prism geometry was isolated by the reaction of polymeric {(HNEt3)2Ag10(tBuC6H4S)12]}n, 1,6‐bis(diphenylphosphino)hexane, and various silver salts under solvothermal conditions. The structures consist of discrete clusters constructed from a girdling Ag9 twisted trigonal prism with the top and bottom trigonal faces capped by diverse anions (i.e., S2? and CF3SO3? for compound 1 , 2×CF3SO3? for compound 2 , 2×NO3? for compound 3 , and tBuC6H4S? and Mo2O72? for compound 4 ). This trigonal prism is bisected by another shrunken Ag3 trigon at its waist position. Interestingly, two inversion‐related Ag9 trigonal‐prismatic clusters are dimerized by the Mo2O72? ion in compound 4 . The twist is amplified by the bulkier thiolate, which also introduces high steric‐hindrance for the capping ligand, that is, the longer dpph ligand. Four more silver–sulfur clusters (namely, compounds 5 – 8 ) with their nuclearity ranging from 6–10 were solely characterized by single‐crystal X‐ray diffraction to verify the above‐described synergetic effect of mixed ligands in the construction of Ag9 twisted trigonal prisms. Surprisingly, only cluster 1 emits yellow luminescence at λ=584 nm at room temperature, which may be attributed to a charge transfer from the S 3p orbital to the Ag 5s orbital, or mixed with metal‐centered (MC) d10→d9s1 transitions. Upon cooling from 300 to 80 K, the emission intensity was enhanced along with a hypsochromic shift. The good linear relationship between the maximum emission intensity and the temperature for compound 1 in the range of 180–300 K indicates that this is a promising molecular luminescent thermometer. Furthermore, cyclic voltammetric studies indicated that the diffusion‐ and surface‐controlled redox processes were determined for compounds 1 and 3 as well as compound 4 , respectively. |
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| Keywords: | cluster compounds luminescence silver trigonal-prismatism voltammetric behaviors |
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