Enclathrating Benzene in a Neutral Dicopper(II) Coordination Framework

Abstract

Two infinite complexes {[Cu2(O2CCH3)4](3-tpt)(CH3OH)2}∞ (1) and {[Cu2(O2CPh)4](3-tpt)(C6H6)1.5}∞ (2) were obtained by reactions of 2,4,6-tris(3′-pyridyl)-1,3,5-triazine (3-tpt) with Cu2(O2CCH3)4 and Cu2(O2CPh)4, respectively, which have been structurally established by single-crystal X-ray diffraction. Complex (1) consists of one-dimensional zig-zag chains in its solid state, which can encapsulate methanol molecules; complex (2) consists of one-dimensional helical chains in its solid state, providing large channels which can selectively enclathrate benzene molecules. (1) crystallizes in the monoclinic space group P21/c with a 8.2892(4), b 22.8479(8), c 16.9258(10) Å, β 99.1480(10)°, V 3164.8(3) Å3, and Z 4; (2) crystallizes in the triclinic space group P1 with a 10.7641(8), b 12.0908(8), c 18.9039(12) Å, α 82.514(3)°, β 85.268(2)°, γ 79.746(4)°, V 2395.9(3) Å3, and Z 2. The inclusion selectivity toward aromatic molecules was discussed.

Nanotubular Metal−Organic Frameworks with High Porosity Based on T-Shaped Pyridyl Dicarboxylate Ligands

“…Paddlewheel-based MOFs are widely constructed by organic linkers with multiple carboxylate groups including a dicarboxylate linker, tricarboxylate linker (e.g., 1,3,5-benzenetricarboxylic acid), tetracarboxylate linker (e.g., 3,3′,5,5′-biphenyltetracarboxylic acid), hexacarboxylate linker, and so forth. Combined use of carboxylate ligands and diimines has resulted in a number of MOFs, for example, monocarboxylic acid and tripyridine and monocarboxylic acid and tetrapyridine . MOFs based on dicarboxylic acids and bridging diamines/diimines have yielded interesting porous structures, whereas they are normally interpenetrated, thus reducing the porosity …”

Tuning the Structure and Flexibility of Coordination Polymers via Solvent Control of Tritopic Triazine Conformation during Crystallization

“…As explained previously, the main difficulty of forming metal-assemblies involving the 3-tpt linker resides in controlling the orientation of the pyridyl groups prior to coordination to the metal center . Methods for orientation control have not yet been described, but rather a collection of diverse structures with both 3-tpt conformations can be found published. − Table summarizes the extended 3-tpt/metal reported structures together with the compounds synthesized in this work, indicating significant crystallization conditions and the observed conformation for the linker. The summarized data clearly suggest that the symmetric conformation A is favored when aprotic solvents are employed for crystallization, whereas conformation B seems to be preferred when protic solvents are used.…”

“…14 Next, this linker has been intensely used to build nanometersized macrocycles involving asymmetric 3-tpt by layering it in methanol. 15−18 The first examples of 3-tpt CPs entangled the dicopper Cu(II) paddlewheel giving 1D 19 or 3D 20 which the 3-tpt acts as either bidentate (A−B conformations) or tridentate (A conformation), respectively. Cu(I)cyanide 3D CPs have been hydrothermally prepared involving asymmetric 3-tpt.…”

“…3-tpt has been used to build 0D mono- and polynuclear complexes and few 1D–3D CPs. − 3-tpt was first employed to synthesize perchlorometalate salts (MCl 6 , M = Sb, Bi, Fe) in aqueous acid media, in which the N pyridyl positions are disordered across the two possible A–B conformations . Next, this linker has been intensely used to build nanometer-sized macrocycles involving asymmetric 3-tpt by layering it in methanol. − The first examples of 3-tpt CPs entangled the dicopper Cu­(II) paddlewheel giving 1D or 3D products, in which the 3-tpt acts as either bidentate (A–B conformations) or tridentate (A conformation), respectively. Cu­(I)­cyanide 3D CPs have been hydrothermally prepared involving asymmetric 3-tpt .…”