Reaction between 4-aminopyridine and a dinuclear zinc(II) component of a Robson macrocyclic ligand has resulted in the formation of a molecular ladder element motif. X-ray single crystal structural analysis indicates that two pyridine rings are assembled at the same direction of the macrocycle, which are placed in a nearly parallel way via

The condensation between sodium 2,6-diformyl-4-X-phenolate (X=Cl, CH3) with the reduced 1:1 Schiff base of 2,2',2"-tris (aminoethyl) amine (tren) and 2-formylfuran (or benzaldehyde) followed by in situ transmetallation with copper(II) perchlorate results in the production of four novel tetranuclear copper(II) complexes of 2:2 macrocyclic Schiff bases with functional pendant-arms (H2L1-4), which have been spectroscopically characterized. A typical complex (1) has been structurally studied by X-ray diffraction. In the cation of complex 1, [Cu4L1Cl2(OH)2]2+, a chair-shaped Cu4O4 core with two μ3-hydroxide groups inside is composed of two kinds of crystallographicall ndependent Cu(II) atoms, while each possesses a configuration of a distorted square pyramid. The four metal atoms are in an approximate parallelogram. Two pendant-arms, mono-dentatively bonding to their adjacent metal atoms, lie in the 'trans' position of the macrocycle. The variable temperature magnetic susceptibility of 1 has been measured in a temperature rang 4-300K. The best fitting with a quasi-butterfly magnetostructural model shows antiferromagnetic exchanges within this compound, with Jbb=-270.8cm-1, Jwb1=-40.3cm-1 and Jwb2=-37.5cm-1.

A dinuclear manganese macrocyclic complex with functional pendant arms, [Mn2(II)HL2](ClO4), has been prepared by the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-N-(2-hydroxybenzyl)amine and subsequent transmetallation of Mn(II)(ClO4)2. In the molecular structure of the complex, each pendant arm is bound to an adjacent manganese atom and both arms lie on the same side of the resulting tetra-imine macrocycle. Each manganese(II) ion is in a distorted octahedral configuration. The variable-temperature magnetism and the cyclic voltammogram of the complex have also been investigated. In the catalytic study, this compound exhibits a high activity for catalyzing disproportionation of H2O2 to O2.

The aggregation of molecular building blocks via selfassembly has recently been of wide interest because the potential of the ordered network directed either by metal ions or by hydrogen bonds offers opportunities to develop new approaches for functional materials.1 In the former, deliberate designs of transition metals with certain linear bifunctional ligands, e.g., 4,4

The combination of a macrocyclic precursor and a sodium ion, sodium 2,6-diformyl-4-substitutedphenolate, offers an effective template to carry out Schiff base cyclocondensation with a quite number of polyamines. Followed by transmetallation with heavy metals has resulted in the production of several classes of macrocyclic complexes which have been structurally characterized. The ligands are involved with [2+2], [2+3], [3+3] and [4+4] condensation modes of macrocyclic precursors with multi-amines. It has been found so far that the sodium template presents several unique features such as a 'versatile' template regardless of ring sizes, easy replacement by transition metals and induced certain group elimination during the reaction.