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Issue 40, 2013
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Can self-assembly of copper(ii) picolinamide building blocks be controlled?†

Marijana Đaković,*a   Diogo Vila-Viçosa,b   Nuno A. G. Bandeira,b   Maria José Calhorda,*b   Bojan Kozlevčar,c   Zvonko Jagličićde  and  Zora Popović*a  
Author affiliations

* Corresponding authors

a Laboratory of General and Inorganic Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
E-mail: mdjakovic@chem.pmf.hr, zpopovic@chem.pmf.hr
Fax: +385-1-4606-341
Tel: +385-1-4606-356

b Departmento de Química e Bioquímica, CQB, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, Ed. C8, 1749-049 Lisbon, Portugal
E-mail: mjcalhorda@fc.ul.pt
Fax: +351-217500088
Tel: +351-217500196

c Fakulteta za kemijo in kemijsko tehnologijo, Univerza v Ljubljani, Aškerčeva c. 5, 1000 Ljubljana, Slovenia

d Inštitut za matematiko, fiziko in mehaniko, Jadranska c. 19, 1000 Ljubljana, Slovenia

e Fakulteta za gradbenuištvo in geodezijo, Univerza v Ljubljani, Jamova c. 2, 1000 Ljubljana, Slovenia

Abstract

Four copper(II) derivatives with picolinamide (piaH), [Cu(N3)2(piaH)2] (1), [Cu(NCO)2(piaH)2] (2), [Cu(pia)2]·2H2O (3) and [Cu(pia)(piaH)(ClO4)]2 (4) are reported. 1 and 2 were isolated as powders shortly after precipitation, becoming crystalline (3) after prolonged standing in mother liquor. The single crystal X-ray analysis revealed the deprotonation of the amide nitrogen (pia) in both 3 (mononuclear square planar [Cu(pia-N,N)2] building blocks) and 4 (pia acting as a bridge between copper(II) ions within the dimer). MAGSUS χMT versus T curves suggest only weak magnetic interactions between the copper(II) species in 3 and 4, though 4 is dinuclear. The magnetic coupling was reproduced by DFT calculations on the experimentally determined structures. The mechanism of formation of compounds 3 and 4 was analyzed by DFT calculations. Models of 1 and 2 underwent transfer of two hydrogen atoms from the piaH ligands to the two axial ligands N3− or NCO− that were released yielding 3. In the reaction leading to 4, the perchlorate is a very weak base that cannot deprotonate the piaH ligand and after the first hydrogen transfer to acetate the dimer 4 is formed. This reactivity, favoring alternative pathways, may switch off an expected self-assembly process.

Graphical abstract: Can self-assembly of copper(ii) picolinamide building blocks be controlled?

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Article information

https://doi.org/10.1039/C3CE41011K
Submitted
04 Jun 2013
Accepted
04 Jul 2013
First published
08 Jul 2013
CrystEngComm, 2013,15, 8074-8087
Article type
Paper
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Can self-assembly of copper(II) picolinamide building blocks be controlled?

M. Đaković, D. Vila-Viçosa, N. A. G. Bandeira, M. J. Calhorda, B. Kozlevčar, Z. Jagličić and Z. Popović, CrystEngComm, 2013, 15, 8074
DOI: 10.1039/C3CE41011K

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