Nickel(II) and copper(I,II)-based metal-organic frameworks incorporating an extended trispyrazolate linker

Solvothermal reactions between the tritopic pyrazole-based ligand 1,3,5-tris.(1H-pyrazol-4-yl) phenyl) benzene (H3BTPP) and nickel(II) perchlorate or copper(II) nitrate afforded two new metal-organic frameworks, Ni-3(BTPP)(2)center dot solvent(Ni-BTPP) and (Cu4Cu2II)-Cu-I(OH)(2)(BTPP)(2)center dot solvent (Cu-BTPP). Powder diffraction structure determination methods were employed to determine the crystal and molecular structure of the copper(I,II) derivative: triangular [Cu3N6(mu(3)-OH)] nodes are connected to six nearby ones by the pyrazolate ligands, thus constructing flat two-dimensional layers that stack to form slit-like one-dimensional channels. Thermogravimetric analyses highlighted both the thermal stability and the permanent porosity of these two materials. Porosity was confirmed by N-2 adsorption at 77 K, yielding Langmuir specific surface areas of 1923(3) m(2) g(-1) and 874(8) m(2) g(-1) for Ni-BTPP and Cu-BTPP, respectively. Additionally, Ni-BTPP adsorbed 1.73 mmol g(-1) (7.6 wt%) of CO2 at the mild conditions of 298 K and 1 bar.