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Controlling the supramolecular polymerization of dinuclear isocyanide gold(i) arylethynylene complexes through tuning the central π-conjugated moiety

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Abstract

Three dinuclear gold(I) p-arylene(diethynyl) complexes with the same peripheral isocyanide ligation and different central conjugated moieties have been prepared and their supramolecular polymerization was comprehensively studied. The central, core-forming π-conjugated arylene moieties present in the complexes have been shown to exhibit a pronounced influence on the resulting photophysical properties, self-assembly mechanisms, morphologies and gelation behavior of the supramolecular polymers. Complexes 1 and 2 bearing biphenylene and phenylene central chromophores exhibit a cooperative mechanism during the supramolecular polymerization, with the appearance of pronounced low-energy phosphorescence attributed to the aurophilic interactions. In contrast, compound 3 with a central benzothiadiazole moiety was found to undergo self-assembly via an isodesmic mechanism. Due to the presence of stronger π–π interactions, complexes 1 and 3 possess lower ΔG0 values for self-assembly and a stronger tendency to form metallogels. Given the balance between the non-covalent interaction enthalpy of the core-forming moieties and intercoronal chain repulsion, 1 and 3 tend to form one-dimensional fibers, while 2 with a short central chromophore is likely to form zero-dimensional spherical aggregates.

Graphical abstract: Controlling the supramolecular polymerization of dinuclear isocyanide gold(i) arylethynylene complexes through tuning the central π-conjugated moiety

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Article information


Submitted
11 Jan 2020
Accepted
14 Mar 2020
First published
16 Mar 2020

Polym. Chem., 2020, Advance Article
Article type
Paper

Controlling the supramolecular polymerization of dinuclear isocyanide gold(I) arylethynylene complexes through tuning the central π-conjugated moiety

N. Zhou, R. Hailes, Y. Zhang, Z. Chen, I. Manners and X. He, Polym. Chem., 2020, Advance Article , DOI: 10.1039/D0PY00049C

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