期刊
CRYSTALS
卷 9, 期 1, 页码 -出版社
MDPI
DOI: 10.3390/cryst9010036
关键词
cuprophilic interactions; luminescence thermochromism; photocrystalographic studies; solid-state spectroscopy; theoretical calculations; electronic excited states
资金
- National Science Centre in Poland [2014/15/D/ST4/02856]
- DOE Office of Science by Argonne National Laboratory [DE-AC02-06CH11357]
- National Institute of General Medical Sciences of the National Institutes of Health (NIH) [R24GM111072]
- NIH/NIDDK
- Wrocaw Centre for Networking and Supercomputing [285]
A model luminescent [(PhCO2)(4)Cu-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, (CC)-C-3. The emission from this state predicted in TDDFT (similar to 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 similar to 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., [(PhCO2)(6)Cu-6]) 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)(4)Cu-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 [(PhCO2)(6)Cu-6] (Cu-6) complex.
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