Maxwell A. Braverman

Hydrothermal synthesis of divalent metal pyromellitate/dipyridylamine complexes: From an unprecedented supramolecular three-dimensional topology to an anionic coordination polymer framework with large incipient cation-bearing voids

Hydrothermal synthesis has afforded two divalent metal coordination complexes incorporating both fully deprotonated pyromellitate (pyro) anions and the kinked dipodal organodiimine 4,4′-dipyridylamine (dpa), {[Co(H2O)4(Hdpa)2][pyro]} (1) and {[H2dpa][Zn(pyro)]·2H2O} (2). Both new complexes were characterized by single crystal X-ray diffraction and spectral and thermogravimetric analyses. Complex 1 possesses discrete [Co(H2O)4(Hdpa)2]4+ cations linked into supramolecular 2-D (4,4) rhomboid grid layer motifs by hydrogen bonding between the unligated pyro anions and the aquo ligands. The pendant, monodentate Hdpa+ cations also engage in charge-separated hydrogen bonding to pyro anions in neighboring layers, resulting in a supramolecular 3-D structure with an unprecedented 6-connected 446108 topology. In contrast, 2 is a true coordination polymer, with divalent Zn atoms linked by ligated pyro anions into a binodal 4-connected PtS-type anionic network (4284 topology), which encapsulates H2dpa2+ cations and unligated water molecules within large incipient pores coursing through the structure. Irradiation of a solid sample of 2 with ultraviolet light resulted in blue-light emission, likely indicative of π–π* transitions within the orbital manifolds of both the pyro anions and unligated H2dpa2+ cations.

Poly[4,4′-imino­dipyridinium [di-μ4-isophthalato-κ4O:O′:O′′:O′′-di-μ3-iso­phthal­ato-κ3O:O′:O′′;κ4O:O′:O′′,O′′′-trizinc(II)] dihydrate]

In the title compound, {(C10H11N3)[Zn3(C8H4O4)4]·2H2O}n, divalent Zn atoms are linked into trinuclear units featuring tetrahedral, octahedral and distorted tetrahedral, octahedral and square-pyramidal coordination geometries. These trinuclear units are connected by isopthalate dianions into [Zn3(isophthalate)4]n 2n− anionic layers, which aggregate into the three-dimensional structure via hydrogen-bonding pathways mediated by doubly protonated 4,4′-iminodipyridinium cations and water molecules of crystallization. One solvent water molecule was found to be disordered over two positions, each with a 50% site-occupancy factor.