General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

Abstract

A general class of C3 -symmetric Ag9 clusters, [Ag9 S(tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )] (1), [Ag9 (tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )2 ]⋅CF3 SO3 (2), [Ag9 (tBuC6 H4 S)6 (dpph)3 (NO3 )2 ] ⋅NO3 (3), and [Ag9 (tBuC6 H4 S)7 (dpph)3 (Mo2 O7 )0.5 ]2 ⋅2 CF3 COO (4) (dpph=1,6-bis(diphenylphosphino)hexane), with a twisted trigonal-prism geometry was isolated by the reaction of polymeric {(HNEt3 )2 [Ag10 (tBuC6 H4 S)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., S(2-) and CF3 SO3 (-) for compound 1, 2×CF3 SO3 (-) for compound 2, 2×NO3 (-) for compound 3, and tBuC6 H4 S(-) and Mo2 O7 (2-) 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 Mo2 O7 (2-) 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) d(10) →d(9) s(1) 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.

A Water-Stable Cl@Ag14 Cluster Based Metal–Organic Open Framework for Dichromate Trapping and Bacterial Inhibition

“…Their fascinating argentophilic interactions not only contribute to the formation of aggregation of silver atoms but also have important influences on the luminescence properties. − The Zang group reported a Ag 31 cluster based a 2D layer formed through the linkage of NO 3 – . Our group has long been pursuing the synthesis of novel silver clusters and related extended frameworks, − and very recently, we isolated the first 3D 2-fold interpenetrated dia open framework based on a sulfate-templated Ag 22 cluster . Although there are some examples, how they are built from solution is still difficult to understand.…”

Heterometallic–Organic Framework from [Cu2I2] and [PbO]n Chains: Photoluminescence, Sensing, and Photocatalytic Performance

“…The relationship can be fitted as the equation I / I 77 K = −0.0033 T + 1.1947 with an R 2 value of 0.985. Remarkably, the temperature identification range (77–300 K) of compound 1 is much wider than that of other previously reported luminescent MOFs, − suggesting that the title Cu–Pb-based heterometallic MOF can be deemed to be a superior intensity-dependent luminescent ratiometric thermometer.…”

Three New Supramolecular Coordination Polymers Based on 1H-pyrazolo[3,4-b]pyridin-3-amine and 1,3-benzenedicarboxylate Derivatives

“…These nine metal ions are arranged in a quasi-linear form of Zn1-Zn2-Zn4-Zn3-Zn5-Zn3a-Zn4a-Zn2a-Zn1a ( a = 2 − x , 1 − y , − z ), forming a {Zn 9 (L) 8 ( μ 2 -OH) 4 (OCO) 2} secondary building unit ({Zn 9 } unit), as shown in Figure 11. Although some nonanuclear polymers have been reported [26,27,28,29], most of them are based on rare earth ions [27,30,31,32], while those based on the Zn(II) ion are relatively rare [33,34]. Furthermore, most of the reported structures of nonanuclear units are a square antiprismatic arrangement or hourglass structure [33,35].…”