Premium
Synthesis and Structural Flexibility of a Series of Copper(II) Azolate‐Based Metal–Organic Frameworks
Author(s) -
Sumida Kenji,
Foo Maw Lin,
Horike Satoshi,
Long Jeffrey R.
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000490
Subject(s) - chemistry , molecule , steric effects , octahedron , metal organic framework , solvent , copper , metal , crystallography , linker , organic molecules , ion , thermal stability , topology (electrical circuits) , inorganic chemistry , stereochemistry , crystal structure , organic chemistry , adsorption , mathematics , combinatorics , computer science , operating system
The reaction of CuCl 2 · 2H 2 O with three novel ditopic ligands, 2‐methyl‐1,4‐benzeneditetrazolate (MeBDT 2– ), 4,4′‐biphenylditetrazolate (BPDT 2– ), and 2,3,5,6‐tetrafluoro‐1,4‐benzeneditriazolate (TFBDTri 2– ), affords the metal–organic frameworks Cu(MeBDT)(dmf) ( 1 ), Cu(BPDT)(dmf) ( 2 ), and Cu(TFBDTri)(dmf) ( 3 ), respectively. These materials feature a common network topology in which octahedral Cu 2+ ions are bridged by azolate ligands and dmf molecules to form one‐dimensional chains. The individual chains are connected by the organic bridging units to form diamond‐shaped channels, in which the solvent molecules project into the pores. The bridging dmf molecules in 1 are readily displaced by other coordinating solvent molecules, which leads to a change in the pore dimensions according to the steric bulk of the solvent. Interestingly, attempts to exchange the analogous solvent molecules in the expanded framework 2 induced no change in the pore size, revealing the rigidity of the framework. Meanwhile, 3 exhibits modest flexibility and an improved thermal stability consistent with its chemical functionality. The marked difference in flexibility highlights the considerable impact the organic linker can have on the dynamic framework properties.