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Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag12}‐in‐{W76} Polyoxometalates under Supramolecular Control 下载免费PDF全文
Caihong Zhan Jamie M. Cameron Jing Gao Jamie W. Purcell De‐Liang Long Leroy Cronin 《Angewandte Chemie (International ed. in English)》2014,53(39):10362-10366
We report the time‐resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one‐pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self‐organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}‐in‐{W76} cluster‐in‐cluster in compound 1 , which further aggregates to cluster compounds 2 and 3 by supramolecular Ag‐POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI‐MS. Further, control experiments demonstrate the crucial role that TeO32?, Cl?, and Ag+ play in the self‐assembly of compounds 1 – 3 . 相似文献
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Dr. Beñat Artetxe Dr. Santiago Reinoso Dr. Leire San Felices Prof. Luis Lezama Prof. Juan M. Gutiérrez‐Zorrilla Dr. Cristian Vicent Fadi Haso Prof. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4616-4625
A series of nine [Sb7W36O133Ln3M2(OAc)(H2O)8]17? heterometallic anions ( Ln3M2 ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9O33} capping unit formed by a planar {MW6O24} fragment to which three {WO2} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW6O24} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln3M2 anions possess chirality owing to a {Sb4O4} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce3Co2 derivative. 相似文献
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