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Achieving tailorable gated adsorption by tuning the dynamic behavior of a host porous material is of great interest because of its practical application in gas adsorption and separation. Here we devise a unique cation-exchange approach to tune the dynamic behavior of a flexible anionic framework, [Zn2(bptc)(datrz)]− (denoted as MAC-6, where H4bptc = [1,1′-biphenyl]-3,3′,5,5′-tetracarboxylic acid and Hdatrz = 3,5-diamine-1H-1,2,4-triazole), so as to realize the tailorable gated adsorption. The CO2 adsorption amount at 273 K can be enhanced by exchanging the counterion of protonated dimethylamine (HDMA+) with tetraethylammonium (TEA+), tetrabutylammonium (TBA+), and tetramethylammonium (TMA+), where the adsorption behavior is transferred from nongated to gated adsorption. Interestingly, the Pgo for gate-opening adsorption can be further tuned from 442 to 331 mmHg by simply adjusting the ratio of HDMA+ and TMA+. The origin of this unique tunable property, as revealed by X-ray diffraction experiments and stru...

Herein, we present a new method for preparing homoligand 3D coordination polymers. First, a layered metal-organic framework Zn3(BDC)3(H2O)2 x 4DMF 1 (BDC is terephthalate, DMF is N,N-dimethylformamide) was fabricated from a H2BDC by liquid-liquid diffusion. Second, the layered product, 1, was used as a precursor to solvothermally react with further H2BDC at 140-180 degrees C, resulting in two products of BDC insertion into the layered structure. These are [Zn3(p-BDC)4] x 2HPIP, 2 (HPIP is partly protonated piperazine), and [Zn3(p-BDC)3(H2BDC)] x (C6H15NO) x H2O x 3DMF, 3 (C6H15NO is triethylamine N-oxide). Single-crystal X-ray diffraction shows that 2 possesses a layer-pillared structure of mu4-BDC, with 1D channels, while 3 has a layer-pillared structure of mu2-BDC, with 2D channels. N2-sorption experiments show 3 has a relatively high BET surface area of 750 m(2)/g. It is proposed that 2 follows the crystal growth mechanism of Ostwald ripening, whereas the crystal structure of 3 might be formed by an insertion mechanism.

Two 3D chiral multifunctional microporous MOFs, Zn3(BTC)2(DMF)3(H2O).(DMF)(H2O) (1) and Cd(4)(BTC)3(DMF)2(H2O)2.6(H2O) (2) (H(3)BTC = 1,3,5-benzenetricarboxylic acid and DMF = N,N'-dimethylformamide), have been synthesized in the presence of organic bases tributylamine (TBA) and triethylamine (TEA), respectively. 1 (C(30)H(38)N(4)O(18)Zn(3)) crystallizes in the tetragonal P4(1)2(1)2 space group (a = 13.6929(19) A, c = 50.664(10) A, V = 9499(3) A(3), and Z = 8). 2 (C33H39N2O28Cd4) crystallizes in the tetragonal P4(3)22 space group (a = 10.3503(4) A, c = 52.557(3) A, V = 5630.4(4) A(3), and Z = 4). X-ray crystallography reveals that 1 consists of a 3D open framework with the (6(3))(4)(6(2).8(2).10(2))(6.(4)8(2))(2) topology, but 2 exhibits a 3D open network with the (4(2).5)(2)(4.(4)5.(10)6.(8)7.(4)8(2)) topology. The solid-state excitation-emission spectra show that the strongest excitation peaks for 1 and 2 are at 341 and 319 nm, and their emission spectra mainly show strong peaks at 410 and 405 nm, respectively. The amounts adsorbed of 1 (2) are 169 mg/g (126 mg/g) for H2O, 137 mg/g (102 mg/g) for C2H5OH, and 133 mg/g (99 mg/g) for CH3OH, which are equivalent to the adsorption of about 62 (34) H2O, 20 (11) C2H5OH, and 28 (16) CH3OH per unit cell, respectively.

A new dirhodium(II,II) paddlewheel complex, [Rh(2)(O(2)CC(6)H(4)COOC(2)H(5))(4)] (1), has been synthesized using a predesigned functionalized carboxylate, namely, 4-(ethoxycarbonyl)benzoate. The target product has been crystallized from the acetone solution and structurally characterized as a bis-acetone adduct, [Rh(2)(O(2)CC(6)H(4)COOC(2)H(5))(4)(OCMe(2))(2)]·C(6)H(14) (2). By utilizing the ability of dangling ester groups to coordinate to open axial ends of neighboring dirhodium units, 1 can self-assemble to form 2D networks upon crystallization from solutions of noncoordinating solvents such as chlorobenzene and chloroform. The resulting [Rh(2)(O(2)CC(6)H(4)COOC(2)H(5))(4)]·2C(6)H(5)Cl (3) and [Rh(2)(O(2)CC(6)H(4)COOC(2)H(5))(4)]·2CHCl(3) (4) products have microporous solid state structures with the pores filled with the corresponding disordered solvent molecules. Notably, 3 and 4 represent unique examples of 2D extended frameworks based on dirhodium tetracarboxylate paddlewheel units devoid of any exogenous ligands. In solution, the dangling ends of carboxylate bridges of 1 have been successfully utilized for condensation reaction with the selected solid support, benzylamine-functionalized polystyrene, allowing successful heterogenization of dirhodium units through the equatorial covalent attachment to the substrate. The resulting solid product was tested as a catalyst in the cyclopropanation reaction of styrene with methyl phenyldiazoacetate to show good yields and diastereoselectivity.