Xiang-Kai Yang

Entanglement in Co(II) coordination networks: polycatenation from single net to 2-fold and 3-fold interpenetrated nets

The synthesis, structures and properties of six coordination networks based on N,N′-di(4-pyridyl)suberoamide (L) and angular dicarboxylate ligands, {[Co(L)(MBA)]·2H2O}n (H2MBA = diphenylmethane-4,4′-dicarboxylic acid), 1, {[Co(L)0.5(MBA)]·CH3OH}n, 2, [Co(L)0.5(MBA)]n, 3, {[Co2(L)(OBA)2]·7CH3OH}n [H2OBA = 4,4′-oxybis(benzoic acid)], 4, {[Co(L)(hfipbb)]·2H2O}n [H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid)], 5, and {[Co(L)(SDA)]·H2O}n (H2SDA = 4,4′-sulfonyldibenzoic acid), 6, are reported. Complex 1 is a 1D → 2D polycatenane derived from the helical channels, whereas both complexes 2 and 3 show 2D layers with the (42·68·8·104)(4)2-2,6L1 topology, which are further entangled to form a 2-fold 2D → 2D interpenetration network and a 2D → 3D inclined polycatenation network, respectively, and complex 4 shows a 3-fold 3D → 3D interpenetration network with the (412·63)-pcu topology. The unusual topological features of 5 and 6 consist of 2- and 3-fold interpenetrated layers with the (44·62)-sql topology, which are further catenated to the two such adjacent sheets in parallel and uniform fashions to give 2D → 3D polycatenated networks. Complexes 1, 5 and 6 represent unique examples that the angular dicarboxylate ligands show significant effect on the degree of interpenetration of polycatenation coordination networks with interpenetrating modes. The CO2 capture is preferable to N2 and H2 in the gas sorption for the desolvated product of 4.

Hg(II) Coordination Polymers Based on N,N'-bis(pyridine-4-yl)formamidine

Reactions of N,N’-bis(pyridine-4-yl)formamidine (4-Hpyf) with HgX2 (X = Cl, Br, and I) afforded the formamidinate complex {[Hg(4-pyf)2]·(THF)}n, 1, and the formamidine complexes {[HgX2(4-Hpyf)]·(MeCN)}n (X = Br, 2; I, 3), which have been structurally characterized by X-ray crystallography. Complex 1 is a 2D layer with the {44·62}-sql topology and complexes 2 and 3 are helical chains. While the helical chains of 2 are linked through N–H···Br hydrogen bonds, those of 3 are linked through self-complementary double N–H···N hydrogen bonds, resulting in 2D supramolecular structures. The 4-pyf- ligands of 1 coordinate to the Hg(II) ions through one pyridyl and one adjacent amine nitrogen atoms and the 4-Hpyf ligands of 2 and 3 coordinate to the Hg(II) ions through two pyridyl nitrogen atoms, resulting in new bidentate binding modes. Complexes 1–3 provide a unique opportunity to envisage the effect of the halide anions of the starting Hg(II) salts on folding and unfolding the Hg(II) coordination polymers. Density function theory (DFT) calculation indicates that the emission of 1 is due to intraligand π→π * charge transfer between two different 4-pyf- ligands, whereas those of 2 and 3 can be ascribed to the charge transfer from non-bonding p-type orbitals of the halide anions to π * orbitals of the 4-pyf- ligands (n→π *). The gas sorption properties of the desolvated product of 1 are compared with the Cu analogues to show that the nature of the counteranion and the solvent-accessible volume are important in determining their adsorption capability.

Mg(II) Coordination Polymers Based on Flexible Isomeric Tetracarboxylate Ligands: Syntheses, Structures, Structural Transformation and Luminescent Properties

By using a new flexible tetracarboxylic acid, bis(3,5-dicarboxyphenyl) adipoamide, H4L1, and its isomer, bis(2,5-dicarboxyphenyl)adipoamide, H4L2, three Mg(II) coordination polymers, {[Mg2(L1)(H2O)2]·2EtOH·3H2O}n, 1, [Mg2(L1)(H2O)8]n, 2, and {[Mg2(L2)(H2O)6]·H2O}n, 3, have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1 and 2 are the solvent ratio-dependent hydrothermally stable products. The tetracarboxylate ligand of complex 1 connects eight Mg(II) ions through nine oxygen atoms, resulting in a three-dimensional (3D) 5-connected uninodal net with a rare non-interpenetrating (44.66)-pcu-5-Pmna topology, whereas those of 2 and 3 link four Mg(II) ions through four oxygen atoms and six Mg(II) ions through six oxygen atoms, forming a 1D linear chain and a 3,6-connected 2-nodal 3D net having {4.62}2{42.610.83}-rtl topology, respectively. Complex 1 shows a series of structural transformations on heating to 200 °C and almost reversible structural transformation when the activated products were immersed in a mixture of ethanol and water or on hydrothermal. Likewise, complex 2 exhibits a reversible structural transformation on heating/hydrothermal, while 3 exhibits irreversible structural transformations. All three complexes exhibit blue light emissions, with that of complex 3 being much more intense.

Dinitrogen-supported coordination polymers

The one-pot solvothermal reactions of 3- and 4-(aminomethyl)pyridine with triethyl orthoformate and Cu(O2CCH3)2 in methanol saturated with dinitrogen afforded the first examples of coordination polymers that are supported by dinitrogen, namely [Cu2.5(3-mpyf)(N2)1.5]n [3-Hmpyf = N,N′-bis(pyridine-3-ylmethyl)formamidine], 1, and {[Cu3(4-Hmpyf)(N2)3]·(CH3OH)}n [4-Hmpyf = N,N′-bis(pyridine-4-ylmethyl)formamidine], 2. The dinitrogen anions of 1 adopt the end-on-dinuclear (μ-η1:η1) bonding mode, resulting in a 4,4-connected binodal net with the new (53·73)2(54·82) topology, and those of 2 display both end-on-dinuclear and end-on-trinuclear (μ-η1:η1:η1) bonding modes, forming a 3,8-connected binodal net with the rare (53)4(58·64·78·84·94)2-3,8T16 topology.

Mercury halide coordination polymers exhibiting reversible structural transformation

Solvothermal reactions of HgX2 salts with the new bis-pyridyl-bis-amide ligand 2,2′-(1,3-phenylene)-bis(N-(pyridin-3-yl)acetamide) (1,3-pbpa) in acetonitrile afforded the complexes [Hg(1,3-pbpa)X2]n (X = Cl, 1; Br, 2; I, 3), while the complexes [Hg(1,3-pbpa)X2·MeCN]n (X = Br, 4; I, 5) were obtained by layering solutions of HgX2 and 1,3-pbpa at room temperature. Complexes 1 and 2 are isostructural one-dimensional (1D) helical chains different from the 1D helical chain 3 in spans, which are 18.0, 18.3 and 29.1 A, respectively. Upon solvent adoption and removal, complexes 2 and 3 undergo reversible structural transformation into the 1D mesohelical chains 4 and 5 with spans of 29.1 and 29.9 A, respectively. Pyridyl ring rotation and amide group reorientation are proposed for the structural transformation accompanied by a simultaneous change in luminescence. The structural transformation in 2 and 4 represents a unique example of elastic 1D helical chains that show stretching during the process. The roles of halide anions in the structural changes and the luminescence properties of 1–5 are also discussed.