Issue 38, 2018

Hierarchical tandem assembly of planar [3×3] building units into {3×[3×3]} oligomers: mixed-valency, electrical conductivity and magnetism

Abstract

A hierarchical tandem assembly – coordination, oligomerisation and supramolecular organization – is identified using MALDI-TOF of the solid products of the solvothermal reaction of 5,5′-pyridyl-3,3′-bi-1H-pyrazole with CuSO4·5H2O in CH3OH–CH3CN. The initial coordination leads to a [3×3] [CuI4CuII5(L)6] (SO4)·2CH3OH (Cu9) grid followed by oligomerisation to a 3×[3×3] [CuI6CuII21(L)18(CN)6(SO4)](SO4)2·8CH3CN (Cu27) grid through bridging sulfate and in situ generated cyanide with time and subsequent supramolecular organization. The isolated silvery lustrous crystals, Cu9 and Cu27, are good electrical conductors, with conductivities of 3.2 × 10−2 and 5.4 × 10−3 S cm−1, respectively, due to the mixed valency. Their magnetic properties are dominated by antiferromagnetic interactions. DFT and band structure calculations confirm their valence distribution and semiconducting behavior. The planarity of the large 3×[3×3] Cu27 and its electro-activity renders it suitable for the development of large surface area molecular devices.

Graphical abstract: Hierarchical tandem assembly of planar [3×3] building units into {3×[3×3]} oligomers: mixed-valency, electrical conductivity and magnetism

Supplementary files

Article information

Article type
Edge Article
Submitted
28 Jūn. 2018
Accepted
27 Jūl. 2018
First published
27 Jūl. 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 7498-7504

Hierarchical tandem assembly of planar [3×3] building units into {3×[3×3]} oligomers: mixed-valency, electrical conductivity and magnetism

F. Yu, M. Kurmoo, G. Zhuang and J. Zuo, Chem. Sci., 2018, 9, 7498 DOI: 10.1039/C8SC02851F

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