Synthesis, structures, DFT studies and properties of novel tertiary diphosphines based on α- and β-naphthylamine

Based on α- and β-naphthylamine, two new diphosphines, N,N-bis((diphenylphos phino)methyl)naphthalen-1-amine ( 1 ) and N,N-bis((diphenylphosphino)methyl)naphthalene -2-amine ( 2 ), have been prepared and characterized by IR, 1 H NMR, 31 P NMR, TG, UV-Vis, XRD and X-ray crystal structure analysis. Structural analysis shows that the two Ph 2 PCH 2 - groups in 1 and 2 are disposed in an anti configuration, and the change of the position of the (Ph 2 PCH 2 ) 2 N-group on the naphthalene moiety results in different spatial configurations of the two Ph 2 P- groups and different weak interactions, such as C-H … π and π–π interactions. DFT studies show that the composition of the HOMOs for 1 and 2 are almost the same (the naphthyl group with admixed N and P atoms), but the ingredients of the LUMOs for 1 are different from that for 2, coinciding with the change of Mülliken atomic charges . Moreover, the emission spectra show that the emissions of complexes 1 and 2 in acetonitrile solution are not similar to those of solid-state samples.