Synthesis, characterization, and green to orange luminescence properties of copper(i) complexes with 3-bdppmapy ligand-containing phenanthroline and its derivatives†

Abstract

This paper presents the successful synthesis of eight Cu(I) complexes 1–8, [Cu(phen)(3-bdppmapy)]BF₄·CH₃OH (1), [Cu(phen)(3-bdppmapy)]ClO₄·CH₃OH (2), [Cu(phen)(3-bdppmapy)]I (3), [Cu(phen)(3-bdppmapy)]CF₃SO₃ (4), [Cu(2,3-f)(3-bdppmapy)]BF₄·CH₃OH (5), [Cu(2,3-f)(3-bdppmapy)]ClO₄·CH₃OH (6), [Cu(2,3-f)(3-bdppmapy)]I·2CH₃OH (7), and [Cu(2,3-f)(3-bdppmapy)]CF₃SO₃·CH₃OH (8) (3-bdppmapyN,N-bis[(diphenylphosphino)methyl]-3-pyridinamine; phen1,10-phenanthroline; 2,3-fpyrazino[2,3-f][1,10]phenanthroline) exhibiting luminescence properties ranging from green to orange emission. Comprehensive characterization and analysis of their structural and photophysical properties were conducted. The results demonstrate that complexes 1–4 and 5–8 possess the same nitrogen ligand, respectively. However, a notable distinction is observed in their fluorescent luminescence position, with complexes 1–4 exhibiting a pronounced blue-shift relative to complexes 5–8. Further structural analysis demonstrated that the phosphine ligands in complexes 5–8 exhibited markedly disparate spatial configurations and photophysical properties compared to previously studied complexes. This finding demonstrates that the luminescence properties of the complexes can be effectively modulated by the structure of the micromodules. Finally, all the complexes were tested using terahertz time-domain spectroscopy, and the results exhibited a clear regularity, supporting our understanding of the relationship between the structure and photophysical properties of the complexes.