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Issue 21, 2020
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Stabilization of polyiodide networks with Cu(ii) complexes of small methylated polyazacyclophanes: shifting directional control from H-bonds to I⋯I interactions

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Abstract

Ordered polyiodide networks have recently gathered considerable attention as electronic materials, a topic historically dominated by metals. Could we incorporate metal cations into polyiodide frameworks in a controlled manner to simultaneously boost electronic properties and robustness of these materials? Herein we present a first principles study featuring three analogous polyazacyclophanes (L, L-Me, L-Me3), differing only in the extent of N-methylation. We demonstrate (potentiometry, ITC) how they all form the same CuL2+ (L = L, L-Me, L-Me3) complex as prevalent species in solution, so that a level playing field exists where only N-methylation distinguishes them. Then we use them as countercations for polyiodide growth. XRD analysis of the resulting crystals clearly shows that methylation is a valuable tool to gradually shift directional control of subtending pairing preferences from H-bond to I⋯I interactions: this affects global packing and actively incorporates metal centres into polyiodide chains, setting the scene for further developments.

Graphical abstract: Stabilization of polyiodide networks with Cu(ii) complexes of small methylated polyazacyclophanes: shifting directional control from H-bonds to I⋯I interactions

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Article information


Submitted
29 Jul 2020
Accepted
12 Sep 2020
First published
15 Sep 2020

Inorg. Chem. Front., 2020,7, 4239-4255
Article type
Research Article

Stabilization of polyiodide networks with Cu(II) complexes of small methylated polyazacyclophanes: shifting directional control from H-bonds to I⋯I interactions

Á. Martínez-Camarena, M. Savastano, J. M. Llinares, B. Verdejo, A. Bianchi, E. García-España and C. Bazzicalupi, Inorg. Chem. Front., 2020, 7, 4239
DOI: 10.1039/D0QI00912A

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