The structures and magnetic properties of self-assembled copper(II) clusters and grids with the "tritopic" ligands 2poap (a), Cl2poap (b), m2poap (c), Cl2pomp (d), and 2pomp (e) are described [ligands derived by reaction of 4-R-2,6-pyridinedicarboxylic hydrazide (R = H, Cl, MeO) with 2-pyridinemethylimidate (a-c, respectively) or 2-acetylpyridine (d, R = Cl; e, R = H)]. Cl2poap and Cl2pomp self-assemble with Cu(NO3)2 to form octanuclear "pinwheel" cluster complexes [Cu-8(Cl2poap-2H)(4)(NO3)(8)].2OH(2)O (1) and [Cu-8(Cl2pomp-2H)(4)(NO3)(8)].15H(2)O (2), built on a square [2 x 2] grid with four pendant copper arms, using "mild" reaction conditions. Similar reactions of Cl2pomp and 2pomp with CU(CIO4)(2) produce pinwheel clusters [Cu-8(Cl2pomp-2H)(4)(H2O)(8)](ClO4)(8)].7H(2)O (3) and [Cu-8(2pomp-2H)(4)(H2O)(8)](ClO4)(8) (4), respectively. Heating a solution of 1 in MeOH/H2O produces a [3 x 3] nonanuclear square grid complex, [Cu-9(Cl2poap-H)(3)(Cl2poap-2H)(3)](NO3)(9).18H(2)O (5), which is also produced by direct reaction of the ligand and metal salt under similar conditions. Reaction of m2poap with Cu(NO3)(2) produces only the [3 x 3] grid [Cu-9(m2poap-H)(2)(m2poap-2H)(4)](NO3)(8).17H(2)O (6) under similar conditions. Mixing the tritopic ligand 2poap with pyridine-2,6-dicarboxylic acid (picd) in the presence of Cu(NO3)(2) produces a remarkable mixed ligand, nonanuclear grid complex [Cu-9(2poap-H)(4)(picd-H)(3)(Picd-2H)](NO3)(9).9H(2)O (7), in which aromatic pi-stacking interactions are important in stabilizing the structure. Complexes 1-3 and 5-7 involve single oxygen atom (alkoxide) bridging connections between adjacent copper centers, while complex 4 has an unprecedented mixed mu-(N-N) and mu-O metal ion connectivity. Compound 1 (C76H92N44Cu8O50Cl4) crystallizes in the tetragonal system, space group (l4) over bar, with a = 21.645(1) Angstrom, c = 12.950(1) Angstrom, and Z = 2. Compound 2 (C84H88N36O44Cl4Cu8) crystallizes in the tetragonal system, space group l4(1)/a, with a = 21,2562(8) Angstrom, c = 12.7583(9) Angstrom, and Z = 2. Compound 4 (C84H120N28O66Cl8Cu8) crystallizes in the tetragonal system, space group l4(1)/a, with a = 20.7790(4) Angstrom, c = 32.561 (1) A, and Z = 4. Compound 7 (C104H104N46O56Cu9) crystallizes in the triclinic system, space group P (1) over bar, with a = 15,473(1) Angstrom, b = 19.869(2) Angstrom, c = 23.083(2) Angstrom, alpha = 88.890(2)degrees, beta = 81.511(2)degrees, gamma = 68.607(1)degrees, and Z = 2. All complexes exhibit dominant intramolecular ferromagnetic exchange coupling, resulting from an orthogonal bridging arrangement within each polynuclear structure.