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Title: On the Nature of Luminescence Thermochromism of Multinuclear Copper(I) Benzoate Complexes in the Crystalline State

Abstract

A model luminescent [(PhCO 2) 4Cu 4] (Cu 4) 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, 3CC. 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, Cu 4 and Cu 6 (i.e., [(PhCO 2) 6Cu 6]) in the crystalline state were discussed and examined. It appeared that crystal packing may constitute anmore » important factor as far as the lack of luminescence thermochromism in the latter case is concerned. Synopsis: Structure–property relationships characterising a model luminescent [(PhCO 2) 4Cu 4] (Cu 4) 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 2) 6Cu 6] (Cu 6) complex.« less

Authors:
; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1491875
Resource Type:
Journal Article
Journal Name:
Crystals
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2073-4352
Publisher:
MDPI
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Jarzembska, Katarzyna, Hapka, Michał, Kamiński, Radosław, Bury, Wojciech, Kutniewska, Sylwia, Szarejko, Dariusz, and Szczęśniak, Małgorzata. On the Nature of Luminescence Thermochromism of Multinuclear Copper(I) Benzoate Complexes in the Crystalline State. United States: N. p., 2019. Web. doi:10.3390/cryst9010036.
Jarzembska, Katarzyna, Hapka, Michał, Kamiński, Radosław, Bury, Wojciech, Kutniewska, Sylwia, Szarejko, Dariusz, & Szczęśniak, Małgorzata. On the Nature of Luminescence Thermochromism of Multinuclear Copper(I) Benzoate Complexes in the Crystalline State. United States. doi:10.3390/cryst9010036.
Jarzembska, Katarzyna, Hapka, Michał, Kamiński, Radosław, Bury, Wojciech, Kutniewska, Sylwia, Szarejko, Dariusz, and Szczęśniak, Małgorzata. Tue . "On the Nature of Luminescence Thermochromism of Multinuclear Copper(I) Benzoate Complexes in the Crystalline State". United States. doi:10.3390/cryst9010036.
@article{osti_1491875,
title = {On the Nature of Luminescence Thermochromism of Multinuclear Copper(I) Benzoate Complexes in the Crystalline State},
author = {Jarzembska, Katarzyna and Hapka, Michał and Kamiński, Radosław and Bury, Wojciech and Kutniewska, Sylwia and Szarejko, Dariusz and Szczęśniak, Małgorzata},
abstractNote = {A model luminescent [(PhCO2)4Cu4] (Cu4) 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, 3CC. 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, Cu4 and Cu6 (i.e., [(PhCO2)6Cu6]) 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. Synopsis: Structure–property relationships characterising a model luminescent [(PhCO2)4Cu4] (Cu4) 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 [(PhCO2)6Cu6] (Cu6) complex.},
doi = {10.3390/cryst9010036},
journal = {Crystals},
issn = {2073-4352},
number = 1,
volume = 9,
place = {United States},
year = {2019},
month = {1}
}