No abstract

A series of six new cyanide-bridged heterometallic complexes including two tetranuclear T-like Fe(III)Mn(III)(3) compounds, {[Mn(L(1))(H(2)O)](3)[Fe(CN)(5)(1-CH(3)im)]}ClO(4) x 1.5 H(2)O (1) and {[Mn(L(2))(H(2)O)](3)[Fe(CN)(5)(1-CH(3)im)]}ClO(4) x 3 H(2)O (2); two heptanuclear cage-shaped M(III)Mn(III)(6) (M = Fe, Cr) compounds, {[Mn(L(2))(H(2)O)](6)[Fe(CN)(6)]}[Fe(CN)(6)] x 6 CH(3)OH (3) and {[Mn(L(2))(H(2)O)](6)[Cr(CN)(6)]}[Cr(CN)(6)] x 6 CH(3)OH (4); and two two-dimensional M-Mn(III) networks, {[H(3)O][Mn(L(1))](2)[Fe(CN)(6)]} x 2 DMF (5) and {K[Mn(L(1))](2)[Cr(CN)(6)]} x 1.5 CH(3)CN x CH(3)OH (6) (L(1) = N,N-ethylene-bis(3-methoxysalicylideneiminate, L(2) = N,N-ethylene-bis(3-ethoxysalicylideneiminate) have been successfully assembled from three polycyanidemetalates containing five or six cyanide groups and two manganese(III) building blocks containing bicompartmental Schiff base ligands. The cyanide-bridged polynuclear complexes are self-complementary through a coordinated aqua ligand from one complex and the free O(4) compartment from the neighboring complex, giving supramolecular one-dimensional ladders and three-dimensional networks for 1 and 2 and for 3 and 4, respectively. Investigation over magnetic susceptibilities of the six complexes reveals the overall ferromagnetic interactions for complexes 1, 2, 3, and 5 and antiferromagnetic interaction for 4 and 6. Compounds 1-4 show some characteristics of metamagnet behavior at low temperatures due to the relatively strong intermolecular hydrogen-bonding interaction. The two complexes with two-dimensional structure exhibit three-dimensional antiferromagnetic ordering with typical metamagnetic behavior below 8.4 K for 5 and 11.5 K for 6, respectively. The present result appears to add new members to the very few examples of polynuclear clusters exhibiting 3D magnetic ordering relying on intermolecular interactions, to the best of our knowledge, which will be helpful for providing valuable information for the understanding and application of intermolecular hydrogen-bonding interactions in the molecular magnetic materials.

A series of four new coordination polymers, namely, [Co(HL 1 )(μ-4,4 0 -bpy)(H 2 O) 3 ] n 3 (4,4 0 -bpy 4), have been assembled from four asymmetric semirigid multicarboxylate ligands 3-(4-carboxy-phenoxy)phthalic acid (H 3 L 1 ), 3-(2-carboxy-phenoxy)-phthalic acid (H 3 L 2 ), 4-(2-carboxy-phenoxy)-phthalic acid (H 3 L 3 ), and 4-(4-carboxyphenoxy)-phthalic acid (H 3 L 4 ) with the help of 4,4 0 -bipyridine (4,4 0 -bpy) ligand. X-ray single crystal diffraction analysis reveals that compound 1 displays a one-dimensional (1D) zigzag chain structure constructed from 4,4 0 -bpy ligands and partly deprotonated L 1 ligands, which further forms a three-dimensional (3D) supramolecular architecture via hydrogen bonds. Complex 2 possesses a two-dimensional (2D) layered architecture composed of continuous trinuclear Co(II) clusters. Complex 3 also shows a 2D molecular framework assembled from alternate tetranuclear and dinuclear Co(II) clusters bridged by 4,4 0 -bpy or L 3 ligands, and complex 4 exhibits a 3D (4,4)-connected self-penetrating network constructed from ladder-like and fishbone-like subunits. Magnetic studies indicate the spin-orbit coupling of isolated Co(II) in 1 and the overall antiferromagnetic interaction in 2-4.

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.

A new end-on azide-bridged dimeric Mn(III) complex has been synthesized by using the tridentate N-isonicotinamidosalicylaidimine ligand. Magnetic studies show that the complex has a high-spin ground state of S = 4 and is ac out-of-phase frequency-dependent.