Reversible Self-Assembly of Water-Soluble Gold(I) Complexes
Aguiló, Elisabet (Universitat de Barcelona)
Moro, Artur J. (Universidade Nova de Lisboa)
Gavara, Raquel (Universitat de Barcelona)
Alfonso, Ignacio (Institut de Química Avançada de Catalunya)
Pérez, Yolanda (Institut de Química Avançada de Catalunya)
Zaccaria, Francesco (Amsterdam Center for Multiscale Modeling)
Guerra, Célia Fonseca (Leiden University)
Malfois, Marc (ALBA Laboratori de Llum de Sincrotró)
Baucells, Clara (Universitat de Barcelona)
Ferrer García, Montserrat (Universitat de Barcelona)
Lima, João Carlos (Universidade Nova de Lisboa)
Rodríguez Raurell, Laura (Universitat de Barcelona)

Date:	2018
Abstract:	The reaction of the gold polymers containing bipyridyl and terpyridyl units, [Au(C≡CCHN)] and [Au(C≡CCHN)], with the water-soluble phosphines 1,3,5-triaza-7-phosphatricyclo[3. 3. 1. 13. 7]decane and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3. 3. 1]nonane gives rise to the formation of four gold(I) alkynyl complexes that self-assemble in water (HO) and dimethyl sulfoxide (DMSO), through different intermolecular interactions, with an impact on the observed luminescence displayed by the supramolecular assemblies. A detailed analysis carried out by NMR studies performed in different DMSO/deuterated HO mixtures indicates the presence of two different assembly modes in the aggregates: (i) chain assemblies, which are based mainly on aurophilic interactions, and (ii) stacked assemblies, which are based on Au···π and π···π interactions. These different supramolecular environments can also be detected by their intrinsic optical properties (differences in absorption and emission spectra) and are predicted by the changes in the relative binding energy from density functional theory calculations carried out in DMSO and HO. Small-angle X-ray scattering (SAXS) experiments performed in the same mixture of solvents are in agreement with the formation of aggregates in all cases. The aromatic units chosen, bipyridine and terpyridine, allow the use of external stimuli to reversibly change the aggregation state of the supramolecular assemblies. Interaction with the Zn cation is observed to disassemble the aggregates, while encapsulating agents competing for Zn complexation revert the process to the aggregation stage, as verified by SAXS and NMR. The adaptive nature of the supramolecular assemblies to the metal-ion content is accompanied by significant changes in the absorption and emission spectra, signaling the aggregation state and also the content on Zn.
Grants:	Ministerio de Economía y Competitividad CTQ2016-76120-P Ministerio de Economía y Competitividad CTQ2015-65040-P Ministerio de Economía y Competitividad CTQ2015-70117-R Ministerio de Economía y Competitividad CSIC13-4E-2076
Note:	This is an open access article published under an ACS AuthorChoice License. See Standard ACS AuthorChoice/Editors' Choice Usage Agreement - https://pubs.acs.org/page/policy/authorchoice_termsofuse.html
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Published in:	Inorganic chemistry, Vol. 57, Issue 3 (February 2018) , p. 1017-1028, ISSN 1520-510X

DOI: 10.1021/acs.inorgchem.7b02343

12 p, 6.4 MB

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