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Frameworks by Solvent‐Free Synthesis of Rare Earth Chlorides with Molten 1,3‐Benzodinitrile and Tailoring of the Particle Size: ∞ 3 [LnCl 3 {1,3‐C 6 H 4 (CN) 2 }], Ln = Y, Dy, Ho, Er, Yb
Author(s) -
Höller Christoph J.,
MüllerBuschbaum Klaus
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.200900962
Subject(s) - chemistry , nanocrystalline material , lanthanide , crystallography , coordination number , crystal structure , anhydrous , chloride , ligand (biochemistry) , single crystal , organic chemistry , ion , biochemistry , receptor
The solvent‐free melt reactions of anhydrous rare earth trichlorides with molten 1,3‐benzodinitrile [1,3‐C 6 H 4 (CN) 2 , C 8 H 4 N 2 ] result in isophthalonitrile frameworks of the rare earth elements. The particle size of the products can bevaried from the millimeter to the nanometer scale (down to 50–400 nm) depending on the synthesis conditions. Thus, these network structures are among the very few coordination polymers that can be synthesized as nanoparticles. A constitution of 1:1 concerning LnCl 3 /1,3‐C 6 H 4 (CN) 2 is found for Y ( 1 ), Dy ( 2 ), Ho ( 3 ), Er ( 4 ), and Yb ( 5 ) in isotypic ∞ 3 [LnCl 3 {1,3‐C 6 H 4 (CN) 2 }]. The ligand 1,3‐C 6 H 4 (CN) 2 functions both as chemical scissors and replaces chloride linkages by degrading the rare earth chloride structures, and subsequently forms new 3D‐framework structures. They consist of strands of chlorido‐coordinated lanthanide atoms, which are linked in two dimensions by 1,3‐C 6 H 4 (CN) 2 molecules. Compounds 1 – 5 were obtained as single crystals from the melt reaction, and their crystal structures were determined by single‐crystal X‐ray analysis. They can also be obtained as nanocrystalline materials from a ball mill treatment, identified by electron microscopy (REM) and EDX analysis.