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Topological Control in Two-Dimensional Cobalt(II) Coordination Polymers by π–π Stacking Interactions: Synthesis, Spectroscopic Characterization, Crystal Structure, and Magnetic Properties

✍ Scribed by Giannis S. Papaefstathiou; Spyros P. Perlepes; Albert Escuer; Ramon Vicente; Anastasios Gantis; Catherine P. Raptopoulou; Alexandros Tsohos; Vassilis Psycharis; Aris Terzis; Evangelos G. Bakalbassis


Publisher
Elsevier Science
Year
2001
Tongue
English
Weight
445 KB
Volume
159
Category
Article
ISSN
0022-4596

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✦ Synopsis


The reactions of CoX 2 (X ‫؍‬ Br, Cl) with the planar, bidentate bridging ligand 2,1,3-benzothiadiazole (btd) in Me 2 CO led to the 2D coordination polymers +[CoBr 2 (btd)], n (1) and +[CoCl 2 (btd)], n (2). The structure of 1 was determined by singlecrystal X-ray crystallography. Complex 1 (C 6 H 4 Br 2 CoN 2 S, monoclinic, P2 1 /m, a ‫؍‬ 3.742(3), b ‫؍‬ 13.075(9), c ‫؍‬ 9.092(6) A s , ‫؍‬ 90.09(2)3, Z ‫؍‬ 2, +2 , R 1 ‫؍‬ 0.0298, wR 2 ‫؍‬ 0.0793) consists of +[Co( -Br) 2 ], n linear chains running along the a axis linked via -btd ligands along the b axis. The columns of stacked btd molecules present in the crystal structure of the free ligand are maintained in the lattice of 1. XRD data revealed that 2 is isostructural with 1. The magnetic properties of both complexes can be explained by the presence of a very weak ferromagnetic intrachain Co2Co exchange interaction through the ( -X) 2 bridges and a moderate antiferromagnetic Co2Co interaction through the -btd bridges. The new complexes were also characterized by EPR, IR, and UV/VIS spectra, and all data are discussed in terms of the nature of bonding and known structures.