Self-Assembly of Antiferromagnetically-Coupled Copper(II) Supramolecular Architectures with Diverse Structural Complexities

The self-assembly of 2,6-diformyl-4-methylphenol (DFMP) and 1-amino-2-propanol (AP)/2-amino-1,3-propanediol (APD) in the presence of copper(II) ions results in the formation of six new supramolecular architectures containing two versatile double Schiff base ligands (H(3)L and H(5)L1) with one-, two-, or three-dimensional structures involving diverse nuclearities: tetranuclear [Cu(4)(HL(2−))(2)(N(3))(4)]·4CH(3)OH·56H(2)O (1) and [Cu(4)(L(3−))(2)(OH)(2)(H(2)O)(2)] (2), dinuclear [Cu(2)(H(3)L1(2−))(N(3))(H(2)O)(NO(3))] (3), polynuclear {[Cu(2)(H(3)L1(2−))(H(2)O)(BF(4))(N(3))]·H(2)O}(n) (4), heptanuclear [Cu(7)(H(3)L1(2−))(2)(O)(2)(C(6)H(5)CO(2))(6)]·6CH(3)OH·44H(2)O (5), and decanuclear [Cu(10)(H(3)L1(2−))(4)(O)(2)(OH)(2)(C(6)H(5)CO(2))(4)] (C(6)H(5)CO(2))(2)·20H(2)O (6). X-ray studies have revealed that the basic building block in 1, 3, and 4 is comprised of two copper centers bridged through one μ-phenolate oxygen atom from HL(2−) or H(3)L1(2−), and one μ-1,1-azido (N(3)(−)) ion and in 2, 5, and 6 by μ-phenoxide oxygen of L(3−) or H(3)L1(2−) and μ-O(2−) or μ(3)-O(2−) ions. H-bonding involving coordinated/uncoordinated hydroxy groups of the ligands generates fascinating supramolecular architectures with 1D-single chains (1 and 6), 2D-sheets (3), and 3D-structures (4). In 5, benzoate ions display four different coordination modes, which, in our opinion, is unprecedented and constitutes a new discovery. In 1, 3, and 5, Cu(II) ions in [Cu(2)] units are antiferromagnetically coupled, with J ranging from −177 to −278 cm(−1).