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  Copper 1D coordination polymers and dimers: Role of the carboxylate and the ammonium cation, crystal structures and magnetic studies.

Rigamonti, L., Carlino, S., Halibi, Y., Demartin, F., Castellano, C., Ponti, A., et al. (2013). Copper 1D coordination polymers and dimers: Role of the carboxylate and the ammonium cation, crystal structures and magnetic studies. Polyhedron, 53, 157-165. doi:10.1016/j.poly.2013.01.016.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0013-786D-7 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0027-CA34-4
Genre: Journal Article

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 Creators:
Rigamonti, L., Author
Carlino, S., Author
Halibi, Y., Author
Demartin, F., Author
Castellano, C., Author
Ponti, A., Author
Pievo, R.1, Author              
Pasini, A., Author
Affiliations:
1Research Group of Electron Paramagnetic Resonance, MPI for Biophysical Chemistry, Max Planck Society, ou_578606              

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Free keywords: Copper carboxylates; Paddle-wheel units; 1D coordination polymers; Hydrogen bond networks; X-ray structures; Magnetic interactions
 Abstract: The 1D coordination polymers [Cu2(syn,syn-η1:η1:μ-RCOO)4(anti,anti-η1:η1:μ-RCOO)(Et3NH)]n, R = Me (1) and H (2), and the dimer [Cu2(syn,syn-η1:η1:μ-PhCOO)4(anti-η1-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-η1:η1:μ-MeCOO)4(anti-η1-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-η1:η1:μ 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-η1-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-η1:η1:μ 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 (−2JŜ1·Ŝ2 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).

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Language(s): eng - English
 Dates: 2013-01-292013-04-10
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1016/j.poly.2013.01.016
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Title: Polyhedron
Source Genre: Journal
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Pages: - Volume / Issue: 53 Sequence Number: - Start / End Page: 157 - 165 Identifier: -