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Tunable trimers: Using temperature and pressure to control luminescent emission in gold(i) pyrazolate-based trimers

Woodall, C.H., Fuertes, S., Beavers, C.M., Hatcher, L.E., Parlett, A., Shepherd, H.J., Christensen, J., Teat, S.J., Intissar, M., Rodrigue-Witchel, A., and others. (2014) Tunable trimers: Using temperature and pressure to control luminescent emission in gold(i) pyrazolate-based trimers. Chemistry - A European Journal, 20 (51). pp. 16933-16942. ISSN 09476539 (ISSN). (doi:10.1002/chem.201404058) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided) (KAR id:50811)

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Abstract

A systematic investigation into the relationship between the solid-state luminescence and the intermolecular AuAu interactions in a series of pyrazolate-based gold(I) trimers; tris(μ2-pyrazolato-N,N')-tri-gold(I) (1), tris(μ2-3,4,5- trimethylpyrazolato-N,N')-tri-gold(I) (2), tris(μ2-3-methyl-5- phenylpyrazolato-N,N')-tri-gold(I) (3) and tris(μ2-3,5-diphenylpyrazolato- N,N')-tri-gold(I) (4) has been carried out using variable temperature and high pressure X-ray crystallography, solid-state emission spectroscopy, Raman spectroscopy and computational techniques. Single-crystal X-ray studies show that there is a significant reduction in the intertrimer AuAu distances both with decreasing temperature and increasing pressure. In the four complexes, the reduction in temperature from 293 to 100 K is accompanied by a reduction in the shortest intermolecular AuAu contacts of between 0.04 and 0.08 The solid-state luminescent emission spectra of 1 and 2 display a red shift with decreasing temperature or increasing pressure. Compound 3 does not emit under ambient conditions but displays increasingly red-shifted luminescence upon cooling or compression. Compound 4 remains emissionless, consistent with the absence of intermolecular AuAu interactions. The largest pressure induced shift in emission is observed in 2 with a red shift of approximately 630 cm-1 per GPa between ambient and 3.80 GPa. The shifts in all the complexes can be correlated with changes in AuAu distance observed by diffraction. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Item Type: Article
DOI/Identification number: 10.1002/chem.201404058
Additional information: Unmapped bibliographic data: LA - English [Field not mapped to EPrints] J2 - Chem. Eur. J. [Field not mapped to EPrints] AD - Department of Chemistry, University of Bath, Bath, United Kingdom [Field not mapped to EPrints] AD - Lawrence Berkeley National Laboratory, Berkeley, CA, United States [Field not mapped to EPrints] AD - Departement de Chimie, Université de Montréal, Montreal, QC, Canada [Field not mapped to EPrints] DB - Scopus [Field not mapped to EPrints]
Uncontrolled keywords: Aurophilicity, Crystallography, Gold, High pressure, Luminescence, Crystallography, Doppler effect, Emission spectroscopy, Gold, Luminescence, Oligomers, Single crystals, Temperature, Aurophilicity, Computational technique, High pressure, Luminescent emission, Pressure-induced shift, Solid-state emissions, Temperature and pressures, Variable temperature, X ray crystallography
Subjects: Q Science > QD Chemistry > QD473 Physical properties in relation to structure
Divisions: Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Giles Tarver
Date Deposited: 21 Oct 2015 16:05 UTC
Last Modified: 23 Jan 2020 04:10 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/50811 (The current URI for this page, for reference purposes)
Shepherd, H.J.: https://orcid.org/0000-0003-0832-4475
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