Reactions between 2,6-diformyl-4-alkyl(R)-phenol (R = CH3 or C(CH3)(3)) and 1,3-diamino-2-hydroxypropane (1,3-DAP) in the presence of copper(II) salts (Cu(BF4)(2)center dot 6H(2)O, Cu(ClO4)(2)center dot 6H(2)O/H3BO3/Ar) and triethylamine (TEA) in a single pot result in self-assembly of dimeric dodecacopper supramolecular architectures of 30-membered hexatopic macrocyclic ligands (H(6)L4 and H(6)L5) with unique and fascinating structures having the BO33- anion as the central species bonded to all six copper centers in a symmetrical fashion (mu(6)-BO33-). A number of closely related macrocyclic hexacopper complexes are reported: {[Cu-6(L4)(mu(6)-BO3)(mu-H2O)(C3H7NO)(2)(BF4)][BF4](2)center dot 3C(3)H(7)NO}(2) (1) (DMF = C3H7NO), {[Cu-6(L4)(mu(6)-BO3)(mu-C3H7NO)(3)][ClO4](3). 3C(3)H(7)NO}(2) (2), {[Cu-6(L5)(mu(6)-BO3)(mu-OH)(H2O)(3)(C3H7NO)][BF4](2)center dot 6C(3)H(7)NO center dot 4C(2)H(5)OH center dot 2H(2)O}(2) (3), {[Cu-6(L5)(mu(6)-BO3)(mu-CH3OH)(CH3OH)(2)][ClO4](3)center dot 10H(2)O}(2) (4), and {[Cu-6(L5)(mu(6)-BO3)(mu-CH3CO2)(mu-CH3O)(CH3OH)][BF4].13CH(3)OH center dot 8H(2)O}(2) (5). A polymeric side product {[Cu-2(H(2)L2)(CH3OH)(BF4)][BF4]}(n) (6), involving a 2 + 2 macrocydic ligand, was also isolated and structurally characterized. Complex 6 involves dinudear copper(II) units linked through BF4- anions to form a novel 1D single-chain polymeric coordination compound. This appears to be the first report in which a central BO33- species is linked to six copper(II) ions held together by a single macrocyclic ligand through three mu(1,1)-O (BO33-) and three mu(1,3)-O (BO33-) bridges. In complexes 1-5 the BO33- is present in the center of the macrocydic cavity and is bonded to all six metal centers arranged in a benzene-like hexagonal array. In the hexagonal array there are alternate double (mu-alkoxide and mu(1,3)-O(BO33-)) and (p-phenoxide and mu(1,1)-O(BO33-)) bridges between the Cu(II) centers. The symmetrical hexa-bridging nature of mu(6)-BO33- is unprecedented in transition metal complex chemistry, and along with alkomide and phenoxide bridges in the equatorial plane provides effective pathways for an overall antiferromagnetic exchange interaction between six copper(II) centers. In 1, 3, and 5 the BO33- moiety is produced in one step (synthetic) by an unusual copper(II)-macrocycle complex catalyzed hydrolysis of BF4- ion in methanol. In 2 and 4 the central species (BO33-) comes from boric acid (H3BO3) which is added to reaction mixture of Cu(ClO4)(2)/H6L4/H(6)L5 under inert conditions to confirm the identity of the central species.