Synthesis, Spectroscopic Characterization, and Photophysical Studies of Heteroleptic Silver Complexes Bearing 2,9-Bis(styryl)-1,10-phenanthroline Ligands and Bis[(2-diphenylphosphino)phenyl] Ether

Abstract

Three new heteroleptic Ag(I) complexes, labeled as [AgL(POP)]BF4 (1–3), were successfully synthesized and comprehensively characterized. Here, L represents 2,9-bis((E)-4-methoxystyryl)-1,10-phenanthroline (L1), 2,9-bis((E)-4-methylthiostyryl) -1,10-phenanthroline (L2), and 2,9-bis((E)-4-diethylaminostyryl)-1,10-phenanthroline (L3), while POP stands for Bis[(2-diphenylphosphino)phenyl] ether. The stability of these compounds in solution was confirmed through multinuclear 1D (1H, 13C, 31P) and 2D NMR (COSY, NOESY, HMBC, HSQC) spectroscopies. Additionally, their molecular structure was elucidated via X-ray crystallography. The photophysical properties of the complexes were assessed both in the solid state and in solution (dichloromethane). Compounds 1–3 demonstrated moderate emissions in solution, with quantum yields ranging from 11–23%. Interestingly, their solid-state luminescent behavior differed. Large bathochromic shifts (42–75 nm) of the emission maxima and a decrease in quantum yields (2.5–9.5%) were evident, possibly due to the presence of excimers. Compound 3 stands out as a rare example of an Ag(I) red-color emitter.

Keywords

• silver(I) heteroleptic complexes
• X-ray diffraction
• luminescence studies
• ³¹P NMR studies