Fliedel, Christophe, Vitor Rosa, Carla I. M. Santos, Pablo J. Gonzalez, Rui M. Almeida, Clara S. B. Gomes, Pedro T. Gomes, Amelia M. N. D. A. Lemos, Gabriel Aullon, Richard Welter, and Teresa Aviles. "
{Copper(II) complexes of bis(aryl-imino)acenaphthene ligands: synthesis, structure, DFT studies and evaluation in reverse ATRP of styrene}."
{DALTON TRANSACTIONS}. {43} (2014): {13041-13054}.
Abstract{Two new Ar-BIAN Cu(II) complexes (where Ar-BIAN = bis(aryl-imino)acenaphthene) of formulations {[}CuCl2(Mes-BIAN)] (1) (Mes = 2,4,6-Me3C6H2) and {[}CuCl2(Dipp-BIAN)] (2) (Dipp = 2,6-iPr(2)C(6)H(3)) were synthesised by direct reaction of CuCl2 suspended in dichloromethane with the respective ligands Mes-BIAN (L1) and Dipp-BIAN (L2), dissolved in dichloromethane, under an argon atmosphere. Attempts to obtain these compounds by solubilising CuCl2 in methanol and adding a dichloromethane solution of the corresponding ligand, under aerobic conditions, gave also compound 1, but, in the case of L2, the Cu(I) dimer {[}CuCl(Dipp-BIAN)](2) (3) was obtained instead of compound 2. The compounds were fully characterised by elemental analyses, MALDI-TOF mass spectrometry, FT-IR, H-1 NMR and EPR spectroscopic techniques. The solid-state molecular structures of compounds 1-3 were determined by single crystal X-ray diffraction, showing the expected chelation of the Ar-BIAN ligands and two chloride ligands completing the coordination sphere of the Cu(11) centre. In the case of the complex 1, an intermediate coordination geometry around the Cu(II) centre, between square planar and tetrahedral, was revealed, while the complex 2 showed an almost square planar geometry. The structural differences and evaluation of energetic changes were rationalised by DFT calculations. Analysis of the electrochemical behaviour of complexes 1-3 was performed by cyclic voltammetry and the experimental redox potentials for Cu(II)/Cu(I) pairs have been compared with theoretical values calculated by DFT in the gas phase and in dichloromethane and methanol solutions. The complex 1 exhibited good activity in the reverse atom transfer radical polymerisation (ATRP) of styrene.}
Maiti, Biplab K., Luisa B. Maia, Kuntal Pal, Bholanath Pakhira, Teresa Aviles, Isabel Moura, Sofia R. Pauleta, Jose L. Nunez, Alberto C. Rizzi, Carlos D. Brondino, Sabyasachi Sarkar, and Jose J. G. Moura. "
{One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O-2/HO-}."
{INORGANIC CHEMISTRY}. {53} (2014): {12799-12808}.
Abstract{The complex {[}Ph4P](2){[}Cu(bdt)(2)] (1(red)) was synthesized by the reaction of {[}Ph4P]2{[}S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound {[}Ph4P]{[}Cu(bdt)(2)] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O-2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a ``thiyl radical character{''}. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures {[}Cu(I)(bdt(2), 4S(3-{*}))](2-) {[}Cu-II(bdt(2), 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, {[}Cu-III(bd(t)2, 4S(4-))](1-).}
Amado, M. P., F. Pinho, P. Faria, and I. Ramalhete. "
Eco-wall modular solutions for buildings."
9th International Masonry Conference. Guimaraes - ISBN: 978-972-8692-87-2: ICM; Universidade do Minho, 2014.
Amado, Miguel, Fernando Pinho, Paulina Faria, and Inês Ramalhete. "
Eco-wall modular solutions for buildings."
IMC2014 - 9th International Masonry Conference 2014. Universidade do Minho, Guimarães 2014.
Fliedel, C., V. Rosa, C. I. M. Santos, P. J. Gonzalez, R. M. Almeida, C. S. B. Gomes, P. T. Gomes, M. A. N. D. A. Lemos, G. Aullón, R. Welter, and T. Avilés. "
Copper(ii) complexes of bis(aryl-imino)acenaphthene ligands: Synthesis, structure, DFT studies and evaluation in reverse ATRP of styrene."
Dalton Transactions. 43.34 (2014): 13041-13054.
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