A series of 3d-4f heterobimetallic phenylene-bridged Schiff base complexes of the general formula [Zn(μ-L1)Ln-(NO3) 3(S)n] [Ln = La (1), Nd (2), Gd (3), Er (4), Yb (5); S = H2O, EtOH; n = 1, 2; H2L1 = N,N′-bis(3-methoxysalicylidene)phenylene-1,2-diamine] and [Zn(μ-L 2)Ln(NO3)3(H2O)n] [Ln = La (6), Nd (7), Gd (8), Er (9), Yb (10); n = 1, 2; H2L2 = N,N′-bis(3-methoxy-5-p-tolylsalicylidene)phenylene-1,2-diamine] were synthesized and characterized. Complexes 1, 2, 4, and 7 were structurally characterized by X-ray crystallography. At room temperature in CH3CN, both neodymium(III) (2 and 7) and ytterbium(III) (5 and 10) complexes also exhibited, in addition to the ligand-centered emission in the UV-vis region, their lanthanide(III) ion emission in the near-infrared (NIR) region. The photophysical properties of the zinc(II) phenylene-bridged complexes (ZnL 1 and ZnL2) were measured and compared with those of the corresponding zinc(II) ethylene-bridged complexes (ZnL3 and ZnL 4). Our results revealed that, at 77 K, both ligand-centered triplet (3LC) and singlet (1LC) states existed for the ethylene-bridged complexes (ZnL3 and ZnL4), whereas only the 1LC state was detected for the phenylene-bridged complexes (ZnL1 and ZnL2). NIR sensitization studies of [Zn(μ-L′)Nd(NO3)3(H2O)n] (L′ = L1-L4) complexes further showed that Nd 3+ sensitization took place via the 3LC and 1LC states when the spacer between the imine groups of the Schiff base ligand was an ethylene and a phenylene unit, respectively. Ab initio calculations show that the observed differences can be attributed to the difference in the molecular vibrational properties and electron densities of the electronic states between the ethylene- and phenylene-bridged complexes.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry