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Structure, Solution Assembly, Electroconductivity of Nanosized Argento-Organic-Cluster/Framework Templated by Chromate

Abstract

In view of elucidating potential structures and assembly mechanism of silver clusters and silver cluster based metal-organic frameworks, we have prepared four argento-organic-clusters/frameworks where the structures are directed by chromate in the mild solvothermal conditions in the presence of different thiolates. All four structures with tBuC6H4S-, SiBu- and SiPr- consist of three core-shells, an inner CrO42-, an intermediate Ag-S aggregate and finally the protective organic moieties. {(HNEt3)3[Ag(CrO4)4@Ag46(SC6H4tBu)24(CF3COO)18(DMF)4]} (1) is a supertetrahedron with an inner Ag(CrO4)4 tetrahedron shelled by four fused Ag11.5S6 lobes. [(CrO4)5@Ag40(SiBu)27(CF3COO)3]n (2) is an undulated snake-like tube housing the infinite CrO42- tetrahedra. [(CrO4)2@Ag41(SiBu)30(NO3)3(CN)4]n (3) forms uncommon 7-connected kwh network incorporating hexagonal layers of Ag19(SiBu)15 balls with a single inner CrO42- connected by another Ag atom. Both enantiomeric chiral qtz frameworks of [CrO4@Ag20(SiPr)10(Cr2O7)2(COOCF3)4(DMF)4]n (4) were structurally characterized. In 4, Cr2O72- connects the Ag20(SiPr)10 clusters with a trapped CrO42- into a 3D quartz (qtz) structure, where the spherical cluster acts like oxygen and the Cr2O72- takes the place of Si in SiO2. Electrospray ionization mass spectrometry (ESI-MS) analysis of the reaction solutions of 1-4 clearly indicated that i) the Ag(CrO4)4@Ag46 core of 1 can retain its molecular structure intact in solution and ii) the chromate-templated polynuclear silver-thiolate species in solution are important building blocks to construct 1D or 3D motif for 2-4, respectively. The electrochemistry in sulfuric acid and the enhancement of the electrical conductivity upon I2 doping are also reported.

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Publication details

The article was received on 31 Jan 2017, accepted on 10 Mar 2017, published on 20 Mar 2017 and first published online on 20 Mar 2017


Article type: Paper
DOI: 10.1039/C7NR00732A
Citation: Nanoscale, 2017, Accepted Manuscript
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    Structure, Solution Assembly, Electroconductivity of Nanosized Argento-Organic-Cluster/Framework Templated by Chromate

    X. Li, H. Su, M. Kurmoo, C. Tung, D. Sun and L. Zheng, Nanoscale, 2017, Accepted Manuscript , DOI: 10.1039/C7NR00732A

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