Tetranuclear copper(II) complexes containing alpha-(D)-glucose-1-phosphate (alpha-(D)-Glc-1P), [Cu-4(mu-OH){mu-(alpha-(D)-Glc-1P)}(2)-(bpy)(4)(H2O)(2)]X-3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu-4(mu-OH) {mu-(alpha-(D)-Glc-1P)}(2)(phen)(4)(H2O)(2)](NO3)(3) (2) were prepared by reacting the copper(II) salt with Na-2[alpha-(D)-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}(2+) fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu(4)-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C-2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-(D)-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-CA)(2)(bpy)(4)](NO3)(2) [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)(2)] also gave the discrete tetracopper(II) cationic complex [Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-m-C6H4(CH2COO)(CH2COOH))(2)-(bpy)(4)](NO3)(2) (5a) as well as the cluster polymer formulated as {[Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-m-C6H4(CH2COO)(2))-(bpy)(4)](NO3)(2) }(n) (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu-II ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta-(D)-gluconolactone, (D)-glucuronic acid, or (D)-glucaric acid in dimethylformamide resulted in the formation of discrete tetracopper complexes with sugar acids, [Cu-4 {mu-(alpha-(D)-Glc-1P)}(2)(mu-SA)(2)(bpy)(4)](NO3)(2)[SA = (D)-gluconate (6), (D)-glucuronate (7), (D)-glucarateH (8a)]. The structures of 6 and 7 were determined by X-ray crystallography to be almost identical with that of 3 with additional chelating coordination of the C-2 hydroxyl group of (D)-gluconate moieties (6) or the C-5 cyclic O atom of (D)-glucuronate units (7). Those with (D)-glucaric acid and (D)-lactobionic acid afforded chiral one-dimensional polymers, {[Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu(D)-glucarate)(bpy)(4)](NO3)(2)}(n) (8b) and {[Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-(D)-lactobionate)(bpy)(4)(H2O)(2)](N O3)(3)}(n) (9), respectively, in which the (D)-Glc-1P-bridged tetracopper(II) units are connected by sugar acid moieties through the C-1 and C-6 carboxylate O atoms in 8b and the C-1 carboxylate and C-6 alkoxy O atoms of the gluconate chain in 9. When complex 7 containing (D)-glucuronate moieties was heated in water, the mononuclear copper(II) complex with 2-dihydroxy malonate, [Cu(mu-O2CC(OH)(2)CO2)(bpy)] (10), and the dicopper(II) complex with oxalate, [Cu-2(mu-C2O4)-(bpy)(2)(H2O)(2)](NO3)(2) (11), were obtained as a result of oxidative degradation of the carbohydrates through C-C bond cleavage reactions.