Structural and luminescent properties of homo- and heterometallic complexes of La, Li and Na with 2-(2-benzoxyazol-2-yl)phenolate ligands

Abstract

A series of homo and heterometallic La, Li and Na complexes with 2-(2-benzoxyazol-2-yl)phenolate (L) ligands were synthesized using La[N(SiMe3)2]3 and M[N(SiMe3)2] (M = Li, Na) or La(Cp)3 as starting materials for La2(L)6 (1), La2(L)6(bipy) (2), La(L)2Cp(DME) (3), La2Li(L)7 (4), Li(L) (5), Na(L) (6). Photoluminescent (PL) properties of these compounds, staring phenol H(L) as well as previously obtained complex LaNa(L)4(DME)2 (7) were studied at 300 and 77 K. Molecular structure of 2, 3 and 4 were determined by X-ray analysis. All the compounds in THF solution at 300 K upon UV excitation (370 nm) revealed a bright fluorescence in the range 430–460 nm and moderate phosphorescence as a shoulder at about 500 nm. The total quantum yield (QY) is 1–35%. At 77 K all lanthanum compounds (except 3) in THF solution exhibit weak or moderate fluorescence but intense phosphorescence (τ 3.5 – 95.8 ms). The PL spectra of solid samples at 300 K strongly differ from those of solutions, apparently due to the effects of crystal packing, the shape and size of the crystals. The emission of H(L) is most intensive but the PL of 1 has lowest efficiency. It is assumed that phosphorescence occurs from excimers and exciplexes, the formation of which in the compounds studied has been confirmed by X-ray diffraction analysis.