Synthesis, crystal structures, and luminescent properties of phenoxo-bridged heterometallic trinuclear propeller- and sandwich-like Schiff-base complexes.

A series of phenoxo-bridged heterometallic Schiff-base trinuclear complexes Zn-M-Zn [M = Cd(II), Pb(II), Nd(III), Eu(III), Gd(III), Tb(III), and Dy(III)] have been synthesized by a rational structural design based on two symmetrical Schiff-base ligands N,N'-bis(3-methoxysalicylidene)propylene-1,3-diamine (H(2)L(a)) and N,N'-bis(3-methoxysalicylidene)benzene-1,2-diamine (H(2)L(b)). Single X-ray diffraction analysis reveals a similar molecular structure among the eight propeller-like and seven sandwich-type phenoxo-bridged Zn-M-Zn complexes. In the compounds Cd[Zn(L(a))Cl](2) (1), {Cd[Zn(L(b))Cl](2)}.H(2)O (2), {Pb[Zn(L(b))Cl](2)}.2H(2)O (4), {Nd[Zn(L(a))Cl](2)(H(2)O)}.0.5ZnCl(4) .2H(2)O (5), and{M(III)[Zn(L(a))Cl](2)(H(2)O)}.0.5ZnCl(4).2MeOH [M = Eu(7), Gd (9), Tb (11), and Dy (13)], two [Zn(L)Cl](-) units coordinate to the central metal ion as a tetradentate ligand using its four oxygen atoms, forming a two-blade propeller-like left-handed and right-handed chiral Zn-M-Zn configuration despite the racemic nature of the whole complexes. Compounds {Pb[Zn(L(a))Cl](2)}.MeOH (3), {Nd[Zn(L(b))Cl](2)(DMF)(OAc)}.CH(3)CN (6), {Eu[Zn(L(b))Cl](2)(DMF)(OAc)}.CH(3)CN (8), {Gd[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (10), {Tb[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (12), {Dy[Zn(L(b))Cl](2)(DMF)(2)}.Cl.2H(2)O (14), and {Pb[Zn(L(b))Cl](2)}.2H(2)O (15) exhibit a relatively rare sandwich-type structure with a central metal ion clamped by two [Zn(L)Cl](-) units. Photophysical studies indicate that all of the complexes exhibit luminescence both in solution and in solid sate, and there exists an energy transfer from the [Zn(L)Cl](-) unit to the central rare earth ions of Nd(III) (5 and 6), Tb(III) (11), and Dy(III) (for 13). In particular, systematic and comparative investigation of the photophysical properties of these trinuclear complexes reveals that the luminescence properties could easily be tuned by changing the central metal or the Schiff-base ligand.