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On the nature of luminescence thermochromism of multinuclear copper(I) benzoate complexes in the crystalline state.

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dc.abstract.enA model luminescent [(PhCO<sub>2</sub>)<sub>4</sub>Cu<sub>4</sub>] (<b>Cu<sub>4</sub></b>) complex in the crystalline state was investigated via combined crystallographic and spectroscopic techniques contributed substantially by theoretical modelling. The complex appeared to exhibit luminescence thermochromism, i.e., red phosphorescence at room temperature which changes to green when lowering the temperature to 90 K. The low-energy emissive state was assigned as a cluster-centred triplet, <sup>3</sup>CC. The emission from this state predicted in TDDFT (~635 nm) matches the experimental red band observed at 660–715 nm. In contrast, the nature of the high-energy “green” band was less straightforward. The next reached cluster-centred triplet excited state occurred to be energetically close to the experimental value of ~545 nm. The two excited states also exhibit significant metal-to-ligand and ligand-to-metal charge transfer characteristics, especially for solid-state distorted geometries. In both cases the cluster core was expected to become notably contracted when compared to the ground state. Time-resolved photocrystallographic results supported the computationally predicted core contraction upon excitation. Additionally, the differences between the spectroscopic behaviour of the related tetra- and hexanuclear copper(I) complexes, <b>Cu<sub>4</sub></b> and <b>Cu<sub>6</sub></b> (i.e., [(PhCO<sub>2</sub>)<sub>6</sub>Cu<sub>6</sub>]) in the crystalline state were discussed and examined. It appeared that crystal packing may constitute an important factor as far as the lack of luminescence thermochromism in the latter case is concerned. <b>Synopsis:</b> Structure–property relationships characterising a model luminescent [(PhCO<sub>2</sub>)<sub>4</sub>Cu<sub>4</sub>] (<b>Cu<sub>4</sub></b>) complex in the crystalline state were investigated via combined crystallographic and spectroscopic techniques contributed by theoretical modelling, and compared with the properties of the related [(PhCO<sub>2</sub>)<sub>6</sub>Cu<sub>6</sub>] (<b>Cu<sub>6</sub></b>) complex.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorBury, Wojciech
dc.contributor.authorSzczęśniak, Małgorzata M.
dc.contributor.authorSzarejko, Dariusz
dc.contributor.authorKutniewska, Sylwia E.
dc.contributor.authorHapka, Michał
dc.contributor.authorJarzembska, Katarzyna
dc.contributor.authorKamiński, Radosław
dc.date.accessioned2024-01-25T15:46:34Z
dc.date.available2024-01-25T15:46:34Z
dc.date.copyright2019-01-12
dc.date.issued2019
dc.description.accesstimeAT_PUBLICATION
dc.description.financeNie dotyczy
dc.description.number1
dc.description.versionFINAL_PUBLISHED
dc.description.volume9
dc.identifier.doi10.3390/CRYST9010036
dc.identifier.issn2073-4352
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/114832
dc.identifier.weblinkhttps://doi.org/10.3390/cryst9010036
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofCrystals
dc.relation.pages36/1-36/22
dc.rightsCC-BY
dc.sciencecloudnosend
dc.subject.encuprophilic interactions
dc.subject.enluminescence thermochromism
dc.subject.enphotocrystalographic studie
dc.subject.ensolid-state spectroscopy
dc.subject.entheoretical calculations
dc.subject.enelectronic excited states
dc.titleOn the nature of luminescence thermochromism of multinuclear copper(I) benzoate complexes in the crystalline state.
dc.typeJournalArticle
dspace.entity.typePublication