Premium
Formation of 1 D and 3 D Coordination Polymers in the Solid State Induced by Mechanochemical and Annealing Treatments: Bis(3‐cyano‐pentane‐2,4‐dionato) Metal Complexes
Author(s) -
Yoshida Jun,
Nishikiori Shinichi,
Kuroda Reiko
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801627
Subject(s) - chemistry , metal , annealing (glass) , polymer , polymer chemistry , nickel , ligand (biochemistry) , coordination polymer , supramolecular chemistry , metal ions in aqueous solution , crystallography , inorganic chemistry , crystal structure , materials science , organic chemistry , metallurgy , biochemistry , receptor
Bis(3‐cyano‐pentane‐2,4‐dionato) (CNacac) metal complex, [M(CNacac) 2 ], which acts as both a metal‐ion‐like and a ligand‐like building unit, forms supramolecular structures by self‐assembly. Co‐grinding of the metal acetates of Mn II , Co II , Ni II , Cu II and Zn II with CNacacH formed a CNacac complex in all cases: mononuclear complex was formed in the cases of Mn II , Cu II and Zn II , whereas polymeric ones were formed in the cases of Fe II , Co II and Ni II . Subsequent annealing converted the mononuclear complexes of Mn II , Cu II and Zn II to their corresponding polymers as a result of dehydration of the mononuclear complexes. The resultant Mn II , Fe II , Co II , Ni II and Zn II polymeric complexes had a common 3 D structure with high thermal stability. In the case of Cu II , a 1 D polymer was obtained. The Mn II , Cu II and Zn II polymeric complexes returned to their original mononuclear complexes on exposure to water vapour but they reverted to the polymeric complexes by re‐annealing. Co‐grinding of metal chlorides with CNacacH and annealing of the mononuclear CNacac complexes prepared from solution reactions were also examined for comparison. [Mn(CNacac) 2 (H 2 O) 2 ], [M(CNacac) 2 (H 2 O)] (M=Cu II and Zn II ) and [M(CNacac) 2 ] ∞ (M=Mn II , Fe II and Zn II ) are new compounds, which clearly indicated the power of the combined mechanochemical/annealing method for the synthesis of varied metal coordination complexes.