2-Pyridine cyclic triimidazole as a chelating and bridging ligand in mono- and hexa-nuclear Re(I) complexes with emissive properties in solution and in the solid state
Articolo
Data di Pubblicazione:
2023
Citazione:
2-Pyridine cyclic triimidazole as a chelating and bridging ligand in mono- and hexa-nuclear Re(I) complexes with emissive properties in solution and in the solid state / D. Malpicci, D. Maver, D. Maggioni, P. Mercandelli, L. Carlucci, E. Cariati, P. Mussini, M. Panigati. - In: NEW JOURNAL OF CHEMISTRY. - ISSN 1144-0546. - 47:46(2023 Dec 14), pp. 21463-21474. [10.1039/D3NJ02823B]
Abstract:
Two luminescent Re(I) complexes, namely the mononuclear fac-[ReCl(CO)3(TT-Py)] (1) and the hexanuclear [{Re(μ-
Cl)(CO)3(μ-TT-Py)}{Re2(μ-Cl)2(CO)6}]2 (2), have been isolated in high yields by one-pot reaction between [ReCl(CO)5] and
different amounts of nitrogen rich 2-pyridine cyclic triimidazole (TT-Py), which acts as chelating ligand in both derivatives.
The metallo-supramolecular cyclic structure of 2, which can be described as a metallacycle in which two mononuclear units
of 1 act as bridging ligands towards two “Re2(μ-Cl)2(CO)6” fragments, has been confirmed by single crystal X-ray diffraction
analysis. Both complexes have been fully characterized in solution by 1D and 2D multinuclear NMR spectroscopy. 1 and 2
exhibit photoluminescence at room temperature in solution, with a broad unstructured emission in the 530–570 nm range.
The nature of the excited states involved in the electronic absorption spectrum of 1 has been ascertained by a combined
density functional and time-dependent density functional (TD-DFT) study. Both compounds exhibit strong aggregation
induced emission enhancement (AIEE), which is more pronounced for 2 leading to a solid state photoluminescence quantum
yield equal to 2.5% that is one of the highest value ever reported for Re(I) polynuclear metallacycles so far. The versatility of
TT-Py to adopt variegated coordination modes, previously observed for Cu(I) and Cu(II) derivatives, is confirmed supporting
further use of this ligand to obtain new and peculiar emissive mono-, polynuclear and extended coordination systems.
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
D. Malpicci, D. Maver, D. Maggioni, P. Mercandelli, L. Carlucci, E. Cariati, P. Mussini, M. Panigati
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