Issue 16, 2017

Structure, solution assembly, and 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 prepared four argento-organic-clusters/frameworks where the structures were directed by chromate 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 an 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 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 in the solution and (ii) the chromate-templated polynuclear silver–thiolate species in solution are important building blocks to construct the 1D or 3D motif for 2–4. The electrochemistry in sulfuric acid and enhancement of the electrical conductivity upon I2 doping have also been reported.

Graphical abstract: Structure, solution assembly, and electroconductivity of nanosized argento-organic-cluster/framework templated by chromate

Supplementary files

Article information

Article type
Paper
Submitted
31 Jan 2017
Accepted
10 Mar 2017
First published
20 Mar 2017

Nanoscale, 2017,9, 5305-5314

Structure, solution assembly, and 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, 9, 5305 DOI: 10.1039/C7NR00732A

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