Structurally Distinct Metal-Organic and H-Bonded Networks Derived from 5-(6-Carboxypyridin-3-yl)isophthalic Acid: Coordination and Template Effect of 4,4′-Bipyridine

5-(6-Carboxypyridin-3-yl)isophthalic acid (H3L) was utilized as an almost unexplored multifunctional ligand to construct, under hydrothermal conditions, ten new coordination compounds, namely, [Cd(mu(2)-H2L)(2)](n) (1), [Ni(HL)(H(2)biim)(2)] (2), [Mn(mu(2)-HL) (phen)(H2O)](2).2H(2)O (3), {[Mn-3(mu(4)-L)(2)(H2O)(6)].3H(2)O}n (4), {[Co-3(mu(5)-L)(2)(H2O)(6)].2H(2)O}n (5), {[Ni-3(mu(4)-L)(2)(H2O)(6)].2H(2)O}n (6), {[Zn-3(mu(5)-L)(2)(H2O)(4)].2H(2)O}n (7), {[Mn-3(mu 5-L)(2)(H2O)(6)].4H(2)O}n (8), {[Co-3(mu(4)-L)(2)(mu(2)-4,4'-bipy)(H2O)6].2H(2)O}n (9), and {[Ni-3(mu(5)-L)2(H2O)(6)].2H(2)O}n (10), also using an optional auxiliary ligand selected from 2,2'-biimidazole (H2biim), 1,10-phenanthroline (phen), or 4,4'-bipyridine (4,4'-bipy). The obtained compounds 1-10 were analyzed by IR spectroscopy, thermogravimetric and elemental analysis, and single-crystal and powder X-ray diffraction. The structures of the products vary from 3D MOFs (metal-organic frameworks 5 and 7-10) to 2D CPs (coordination polymers 1, 4, and 6) as well as to a discrete 0D monomer 2 and a dimer 3. The latter two are extended by multiple hydrogen bonds into complex 3D supramolecular networks. This structural difference in 1-10 is directed by the kind of metal(II) center, the deprotonation degree of the principal H3L building block, and/or the kind of auxiliary ligand. Notably, an addition of 4,4'-bipy can tune the structures of MOFs 8-10 by the coordination or template effect. Topological classification of metal-organic and H-bonded underlying networks was performed, disclosing a variety of topological nets: sql (in 1), 3,10T3 (in 3), 3,4L83 (in 4 and 6), tcs (in 5, 8, and 10), 3,4,5T95 (in 7), and sra (in 9), as well as a topologically unique network in 2. The magnetic properties (for compounds 3-6, 8-10) and luminescent properties (for compounds 1, 7) were also investigated and discussed. In fact, compound 7 exhibits an intense violet emission in the solid state. Measurements of the magnetic susceptibility indicate interactions of an antiferromagnetic nature between the adjacent metal(II) centers in the compounds 3-6 and 8-10. The obtained products represent the first series of metal-organic compounds assembled from the H3L precursor, thus opening up its application as a new pyridine-tricarboxylate organic block for designing CPs or MOFs.