Copper 1D coordination polymers and dimers: Role of the carboxylate and the ammonium cation, crystal structures and magnetic studies (Articolo in rivista)

Type
Label
  • Copper 1D coordination polymers and dimers: Role of the carboxylate and the ammonium cation, crystal structures and magnetic studies (Articolo in rivista) (literal)
Anno
  • 2013-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1016/j.poly.2013.01.016 (literal)
Alternative label
  • L. Rigamonti, S. Carlino, Y. Halibi, F. Demartin, C. Castellano, A. Ponti, R. Pievo, A. Pasini (2013)
    Copper 1D coordination polymers and dimers: Role of the carboxylate and the ammonium cation, crystal structures and magnetic studies
    in Polyhedron
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • L. Rigamonti, S. Carlino, Y. Halibi, F. Demartin, C. Castellano, A. Ponti, R. Pievo, A. Pasini (literal)
Pagina inizio
  • 157 (literal)
Pagina fine
  • 165 (literal)
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  • http://dx.doi.org/10.1016/j.poly.2013.01.016 (literal)
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  • 53 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • a Università degli Studi di Milano, Dipartimento di Chimica, via C. Golgi 19, 20133 Milano, Italy b Università degli Studi di Modena e Reggio Emilia, Dipartimento di Scienze Chimiche e Geologiche, via Campi 183, 41125 Modena, Italy c Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, via C. Golgi 19, 20133 Milano, Italy d Max Planck Institute for Biophysical Chemistry, Am Faßberg 11, 37077 Göttingen, Germany (literal)
Titolo
  • Copper 1D coordination polymers and dimers: Role of the carboxylate and the ammonium cation, crystal structures and magnetic studies (literal)
Abstract
  • The 1D coordination polymers [Cu2(syn,syn-g1:g1:l-RCOO)4(anti,anti-g1:g1:l-RCOO)(Et3NH)]n, R =Me (1) and H (2), and the dimer [Cu2(syn,syn-g1:g1:l-PhCOO)4(anti-g1-PhCOO)2(Et3NH)2] (3) are formed by reaction of copper carboxylates with the corresponding carboxylic acid and NEt3. Moreover, the compound [Cu2(syn,syn-g1:g1:l-MeCOO)4(anti-g1-MeCOO)2(Et2NH2)2] (4) can be obtained with the use of NHEt2. The crystal structures of 1?CH3CN and 2 comprise linear anionic 1D chains of paddle-wheel copper carboxylates [Cu2(RCOO)4], bridged together by anti,anti-g1:g1:l acetato or formato ions. The negative charges are balanced by hydrogen-bonded triethylammonium countercations, and in compound 1 acetonitrile molecules are hosted in the voids between the chains. In compounds 3 and 4, two anti-g1-benzoato or -acetato anions occupy the apical positions of the paddle-wheel dimers [Cu2(RCOO)4], with Et3NH+ or Et2NH2 + cations balancing the negative charges, without the formation of coordination polymer chains. In compound 4, the dimeric units are held together in a 1D network by hydrogen bonds between the apical carboxylates and the diethylammonium cations. In order to evaluate the effect of the simultaneous presence of syn,syn- and anti,anti-g1:g1:l acetato ions on the Cu-Cu magnetic communication, the magnetic susceptibility of 1 has been measured. Data were fitted to a model based on an alternating chain of copper dimers based on the Heisenberg-Zeeman Hamiltonian (?2J S^ 1?S^ 2 convention). The results show the presence of a strong antiferromagnetic coupling within the dimer 2J1 = ?(310.8 ± 0.1) cm?1 and a weak antiferromagnetic coupling between dimers 2J2 = ?(25 ± 1) cm?1. The latter coupling is significant since its introduction in the fit model leads to a well-behaved error surface and to a ?35% decrease of the sum of squared residuals. The electron paramagnetic resonance (EPR) spectra of powder sample of 1 have been recorded between 5 and 295 K, and they are typical of the triplet state of an antiferromagnetic copper dimer (zero field splitting |D| = 0.34 cm?1). (literal)
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