Premium
A 3D Porous Metal Organic Framework Based on Infinite 1D Nickel(II) Chains with Rutile Topology Displaying Open Metal Sites
Author(s) -
Stylianou Kyriakos C.,
Bacsa John,
Bradshaw Darren,
Rosseinsky Matthew J.
Publication year - 2014
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201400136
Subject(s) - nickel , microporous material , rutile , ligand (biochemistry) , porosity , metal organic framework , molecule , mesoporous material , crystallography , metal , chemistry , materials science , topology (electrical circuits) , adsorption , organic chemistry , catalysis , biochemistry , receptor , mathematics , combinatorics
The reaction of Ni II with a tetra‐benzoate pyrene ligand produces a 3D porous framework based on infinite 1D Ni II chains. The Ni II –O connectivity and the formation of a hydroxo‐bridge (μ 3 ‐OH) responsible for the connection of the central Ni II atoms within the 1D Ni II –(μ 3 ‐OH) 2 –Ni II chains can be straightforwardly compared with the Ti IV –O–Ti IV connectivity seen in TiO 2 . The arrangement of the TBAPy ligand around the 1D rutile‐based chains leads in the generation of a porous framework with two distinct types of pores; based on the chemistries of these two types of pores, one can be labelled as hydrophobic and the other as hydrophilic. The use of different activation methods results in the generation of either a porous framework free of guest molecules or a completely solvent‐free material, in which the terminal H 2 O molecules bound to Ni II were removed, leading thus to a framework with open Ni II sites. CO 2 isotherms collected on both frameworks at 195 K and one barshowed type I isotherms characteristic of microporous materials (BET surface areas for: guest‐free framework: 257(3) m 2 · g –1 ; solvent‐free framework: 362(2) m 2 · g –1 ). The affinity of both networks at zero coverage for both CO 2 and CH 4 was found to be greater when the unsaturated Ni II sites are available within the void space.