Geometrically Mismatched Hydrogen-bonded Framework Composed of Tetratopic Carboxylic Acid.

Porous organic frameworks possessing interactive free sites in the pore have attracted much attention due to their potential to show the site-originated specific functionalities. Herein, we demonstrate that such a framework could be constructed using a concept of geometrically mismatched frameworks composed of phenanthroline-based tetratopic carboxylic acid CP-Phen. Simple recrystallization of CP-Phen yielded a solvent included porous framework CP-Phen-1, in which three of four carboxy groups form hydrogen-bonded dimer to form a ladder-shaped framework, while the remained one does not participate in framework formation due to geometrical mismatch and interacts with solvent molecules through weak hydrogen-bonding. This result implies that our proposed strategy is effective to provide free interactive sites in porous frameworks. Although CP-Phen-1 undergoes two-step structural transformation presumably accompanied by hydrogen-bond rearrangements upon loss of solvent molecules, the activate framework shows good thermal stability up to 360 °C and selective CO2 adsorption.

Comprehensively Understanding Isomorphism and Photoluminescent Nature of Two-Dimensional Coordination Polymers of Cd(II) and Mn(II) with 1,1'-Ethynebenzene-3,3',5,5'-tetracarboxylic Ligand.

Four isomorphic two-dimensional (2D) homo- and heterometallic coordination polymers (CPs), [(Cd xMn1- x)3(HEBTC)2(DMSO)6] with x = 1 (1), 1/3 (2), 0.5 (3), and 2/3 (4) were prepared by conventional one-pot self-assembly approach, using Cd2+ or mixtures of Cd2+ and Mn2+ with 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylic (H4EBTC) under solvothermal conditions. The crystal structures of four isomorphic CPs are composed of center-symmetric trinuclear metal clusters building units linked by HEBTC3- ligands, extending into (3, 6)-connected topological 2D nets. Four CPs are isomorphic to the Mn-CP, [Mn3(HEBTC)2(DMSO)6], we recently reported. The solid-state photoluminescence of 1-4 shows dual emissions at ambient condition, where the emission bands centered at ca. 390 and 562 nm in 1 are assigned to the fluorescence and phosphorescence within HEBTC3- ligand, respectively; however, the emission bands centered at around 397 and 470 nm in 2-4 are attributed to fluorescence, corresponding to electron transition within HEBTC3- ligand and MLCT transition between HEBTC3- ligand and Mn2+ ion. In addition, the origin of isomorphism between 1 and Mn-CP is also discussed.

Dimensionality of luminescent coordination polymers of magnesium ions and 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylic acid modulated by structural inducing agents.

Solvothermal reactions of aromatic 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylic acid (H4EBTC) and Mg2+ salts in the presence of different supporting ligands afforded the coordination polymers [Mg(H2EBTC)(DMF)2(H2O)2] (1), [Mg3(HEBTC)2(H2O)4]·solvent (2) and [Mg2(EBTC)(H2O)5]·solvent (3). The crystal structures of 1-3 were determined by the single crystal X-ray diffraction technique, where CP 1 showed a one-dimensional zigzag MgO6 coordination octahedral chain structure; 2 exhibited a two-dimensional MgO6 coordination octahedral framework with trinuclear [Mg3(COO)6] SBUs, and 3 featured a three-dimensional MgO6 coordination octahedral framework with binuclear [Mg2O(COO)2] SBUs. The various structures in CPs 1-3 of Mg2+ ions with the H4EBTC ligand were ascribed to the conformational flexibility and the coordination mode diversity of the H4EBTC ligand. Interestingly, the zwitterionic supporting ligand 2-aminoterephthalic acid or 4-aminobenzenesulphonic acid played a vital role in the initial formation process of nuclear crystals but only as a structural induction agent, which modulated the dimensionality of these Mg2+-based CPs. Additionally, the three CPs emitted bright blue luminescence at ambient conditions, and the emission lifetimes and absolute quantum yields were also investigated.

Intense greenish phosphorescence emission under ambient conditions in a two-dimensional lead(ii) coordination polymer with a 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate ligand.

In this study, a new two-dimensional Pb2+-based coordination polymer (CP), [Pb2(EBTC)(DMSO)3] (1), where H4EBTC is 1,1'-ethynebenzene 3,3',5,5'-tetracarboxylic acid, was synthesized under solvothermal conditions. Structural analysis reveals that 1 crystallizes in the monoclinic space group C2/m, where two crystallographically different Pb2+ ions show a coordination geometry of bicapped trigonal prisms that are connected to a double-chain by the EBTC4- ligands through carboxylate groups along the b-axis direction, and where successive double chains are held together to form a 2D layer via the Pb1 and Pb2 bicapped trigonal prisms sharing one edge or a triangle face along the c-axis direction. Interestingly, CP 1 emitted intense and long-lived greenish phosphorescence in the solid state at ambient conditions, with a quantum yield of 1.5% and a phosphorescence lifetime of 4.17 ms, and the emission mainly arose from the electron transition within the π-type orbitals of the EBTC4- ligand. The emission bands assignment and photophysical process were further discussed according to the calculation of both the electronic band structures and density of states. This study gives a fresh impetus to achieve coordination polymer-based long-lived phosphorescence materials under ambient conditions.

Surprisingly high quantum yield of emission in a fluorescent coordination polymer with paramagnetic Mn(ii) ions.

A two-dimensional coordination polymer, [Mn3(HEBTC)2(DMSO)6] (1), has been achieved by a solvothermal reaction of Mn2+ with 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylic acid (H4EBTC). The layer of a coordination polymer is composed of trinuclear Mn2+ clusters linked by HEBTC3- ligands to form a (3,6)-connected topological net. CP 1 with paramagnetic Mn2+ ions shows dual emissions centered at 397 and 468 nm in the solid state under ambient conditions with respectable quantum yields of 15.3% (397 nm) and 12.3% (468 nm). The dual emissions arise from n ← π* transition in HEBTC3- and MLCT between HEBTC3- and Mn2+ centers.