Divalent metal diphenate dipyridylamine coordination polymers: Supramolecular polytypism and a rare 5-connected topology based on arc-like hexanuclear clusters

• Published in: Polyhedron Vol. 89; pp. 168 - 181
• Main Authors: Weingartz, Lucas E., Nettleman, Joseph H., Farnum, Gregory A., Staples, Richard J., LaDuca, Robert L.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 29.03.2015
• Subjects: Cluster; Coordination polymer; Crystal structure; Diphenate; Luminescence; Diphenate; Cluster; Coordination polymer; Luminescence; Crystal structure
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2015.01.016

Divalent metal diphenate (dip) coordination polymers incorporating 4,4′-dipyridylamine (dpa) ligand have been synthesized and structurally characterized. {[Cd6(dip)6(H2O)4(dpa)4]·5H2O}n features [Cd6(dip)6(H2O)4] arc-like hexanuclear clusters that link to form a complicated 5-connected 4466nov 3-D topology. [Display omitted] A series of divalent metal diphenate (dip, biphenyl-2,2′-dicarboxylate) coordination polymers incorporating the kinked 4,4′-dipyridylamine (dpa) ligand has been hydrothermally synthesized and structurally characterized via single-crystal X-ray diffraction. {[Zn(dip)(dpa)]·3H2O}n (1) and {[Cu3(dip)3(dpa)3(H2O)3.5]·2H2O}n (2) both display 2-D (4,4) grid topologies. {[Cu(dip)(dpa)]·H2O}n (3), a polytype of 2, possesses a non-interpenetrated 3-D 658 cds topology. {[Ni(dip)(dpa)(H2O)2]·H2O}n (4) has a 2-D grid topology similar to 1 and 2. In contrast, the cadmium congener {[Cd6(dip)6(H2O)4(dpa)4]·5H2O}n (5) features [Cd6(dip)6(H2O)4] arc-like hexanuclear clusters that link together into 1-D cadmium dicarboxylate rods, which are further pillared by dpa ligands to form a complicated 3-D coordination polymer lattice with a very rare 5-connected 4466nov 3-D non-interpenetrated cluster node topology. Thermal properties for all phases are presented, along with luminescent properties for 1 and 5.