Novel conjugated, pyridyl-functionalised triazaphospholes with either tBu or SiMe3 substituents at the 5-position of the N3PC heterocycle have been prepared by a [3+2] cycloaddition reaction and compared with structurally related, triazole-based systems. Photoexcitation of the 2-pyridyl-substituted triazaphosphole gives rise to a significant fluorescence emission with a quantum yield of up to 12 %. In contrast, the all-nitrogen triazole analogue shows no emission at all. DFT calculations indicate that the 2-pyridyl substituted systems have a more rigid and planar structure than their 3- and 4-pyridyl isomers. Time-dependent (TD) DFT calculations show that only the 2-pyridyl-substituted triazaphosphole exhibits similar planar geometry, with matching conformational arrangements in the lowest energy excited state and the ground state; this helps to explain the enhanced emission intensity. The chelating P,N-hybrid ligand forms a ReI complex of the type [(N^N)Re(CO)3Br] through the coordination of nitrogen atom N2 to the metal centre rather than through the phosphorus donor. Both structural and spectroscopic data indicate substantial π-accepting character of the triazaphosphole, which is again in contrast to that of the all-nitrogen-containing triazoles. The synthesis and photophysical properties of a new class of phosphorus-containing extended π systems are described. Mix and match: Hitherto unknown pyridyl-functionalized triazaphospholes have been synthesized by a [3+2] cycloaddition reaction starting from phosphaalkynes and pyridyl-substituted azides (see figure). Both experiments and theoretical calculations established these compounds as novel π-conjugated organophosphorus derivatives for future optoelectronic applications.
- coordination modes
- density functional calculations
ASJC Scopus subject areas
- Organic Chemistry