Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M²⁺ = Fe²⁺, Co²⁺, Zn²⁺, Cd²⁺; tdc^2– = 2,5-thiophenedicarboxylate)

Abstract

A series of isostructural 3D coordination polymers (3)∞[M(tdc)(bpy)] (M(2+) = Zn(2+), Cd(2+), Co(2+), Fe(2+); tdc(2-) = 2,5-thiophenedicarboxylate; bpy = 4,4'-bipyridine) was synthesized and characterized by X-ray diffraction, thermal analysis, and gas adsorption measurements. The materials show high thermal stability up to approximately 400 °C and a solvent induced phase transition. Single crystal X-ray structure determination was successfully performed for all compounds after the phase transition. In the zinc-based coordination polymer, various amounts of a second type of metal ions such as Co(2+) or Fe(2+) could be incorporated. Furthermore, the catalytic behavior of the homo- and heteronuclear 3D coordination polymers in an oxidation model reaction was investigated.

Divalent Metal 2,5‐Thiophenedicarboxylate Coordination Polymers with the Conformationally Flexible Bis(4‐pyridyl­formyl)homopiperazine Ligand

“…[11] In contrast to the more commonly used all-carbon ring aromatic dicarboxylates, fewer coordination polymers built from the aromatic ligand 2,5-thiophenedicarboxylate (tdc, Scheme 1) have been reported. [12][13][14][15][16][17] The tdc ligand is similar to isophthalate,but the five-membered thiophene ring orients…”

“…With the common rigid-rod tethering ligand 4,4Ј-bipyridine (bpy), an isostructural series of 3D coordination polymers of formula [M(tdc)(bpy)] n (M = Zn, Cd, Co, Fe) was generated. [15] A solid solution [Zn 1-x Co x (tdc)(bpy)] n served as an alkene oxidation catalyst in the presence of tert-butylhydroperoxide. [15] Even in cases, where no porosity or catalytic behavior was observed, the tdc ligand could act as a linking agent (4,4) grid layers, but with less common 2D + 2D Ǟ 3D parallel entanglement.…”

“…[15] A solid solution [Zn 1-x Co x (tdc)(bpy)] n served as an alkene oxidation catalyst in the presence of tert-butylhydroperoxide. [15] Even in cases, where no porosity or catalytic behavior was observed, the tdc ligand could act as a linking agent (4,4) grid layers, but with less common 2D + 2D Ǟ 3D parallel entanglement. [16] Employing the very long spanning dipyridylamide ligand propane-1,3-diylbis(piperidine-4,1diyl))bis(pyridin-4-ylmethanone) (4-ppbp) afforded [Ni(tdc)(4ppbp) 2 (H 2 O)] n , which possesses a polycatenated system of 2D + 2D Ǟ 2D parallel interpenetrated 2,6-connected looped layers, derived from the edge-crossed (4,4)IIb net.…”

Structural flexibility of a copper-based metal–organic framework: sorption of C4-hydrocarbons and in situ XRD

“…Since the development of metal-organic frameworks (MOFs) [1][2][3][4] or porous coordination polymers (PCPs) 5,6 in the last couple of decades, this class of materials has gained increasing research interest. The enormous variability of these materials due to different linkers and metal ions or secondary building units (SBUs) allows several applications, e.g., in sensor devices, [7][8][9] in heterogeneous catalysis [10][11][12][13][14] as well as for gas storage [15][16][17][18][19] or gas separation. [20][21][22][23][24][25][26] One of the basic requirements for using such materials in sorption processes is the complete removal of pre-adsorbed solvent molecules and residues remaining from synthesis by pretreatment, i.e., evacuation with or without heating.…”

Coordination polymers based on 1,1′-cobaltocenium dicarboxylate linkers

“…Especially in catalysis the less common approach of heteronuclear (or mixed metal) coordination polymers as catalysts can be useful to enhance both the catalytic activity and the stability of the compounds during the reaction. 6,7 While one metal ion species is mainly responsible for the catalytic activity, meanwhile the other one can stabilize the framework. To reach this aim, 1,1′-cobaltocenium dicarboxylate, ccdc − , as linker is predestined due to the already incorporated cobalt(III) atom in the organometallic scaffold.…”