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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.
- Source :
- New Journal of Chemistry; 12/14/2023, Vol. 47 Issue 46, p21463-21474, 12p
- Publication Year :
- 2023
-
Abstract
- Two luminescent Re(I) complexes, namely mononuclear fac-[ReCl(CO)<subscript>3</subscript>(TT-Py)] (1) and hexanuclear [{Re(μ-Cl)(CO)<subscript>3</subscript>(μ-TT-Py)}{Re<subscript>2</subscript>(μ-Cl)<subscript>2</subscript>(CO)<subscript>6</subscript>}]<subscript>2</subscript> (2), were isolated in high yields by a one-pot reaction between [ReCl(CO)<subscript>5</subscript>] and different amounts of nitrogen-rich 2-pyridine cyclic triimidazole (TT-Py), which acts as a 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 "Re<subscript>2</subscript>(μ-Cl)<subscript>2</subscript>(CO)<subscript>6</subscript>" fragments, was confirmed by single-crystal X-ray diffraction analysis. Both complexes were 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 was ascertained by a combined density functional theory and time-dependent density functional theory (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 of 2.5% that is one of the highest values 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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 11440546
- Volume :
- 47
- Issue :
- 46
- Database :
- Complementary Index
- Journal :
- New Journal of Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 173860880
- Full Text :
- https://doi.org/10.1039/d3nj02823b