Electronic structure and properties of camphorimine Cu(I) coordination polymers |
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| Authors: | Tiago A. Fernandes M. Fernanda N. N. Carvalho Adelino M. Galvão Nuno A. G. Bandeira Maria José Calhorda Ana M. Botelho do Rego |
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| Affiliation: | 1. CQE, Complexo I, Instituto Superior Técnico, Universidade Técnica de Lisboa, Lisboa, Portugal;2. Departamento de Química e Bioquímica, CQB, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, Lisboa 1749‐016, Portugal;3. Departament de Química‐Física i Inorgánica, Universitat Rovira i Virgili, N4 Campus Sescelades, Carrer Marcel·lí Domingo, Tarragona 43007, Spain;4. Centro de Química‐Física Molecular (CQFM) and Institute of Nanoscience and Nanotechnology (IN), Complexo Interdisciplinar, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, Lisboa 1049‐001, Portugal |
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| Abstract: | The first Cu(I) coordination polymer with an aromatic‐substituted camphorimine ligand [(CuCl)(μ‐Cl) (Cu(H2NC6H4NC10H14O)]n was obtained from reaction of CuCl with 3‐(4‐aminophenylimino)‐1,7,7‐trimethylbicyclo[2.2.1]heptan‐2‐one (H2NC6H4NC10H14O). The electronic and the surface properties (studied by X‐ray photoelectron spectroscopy) are consistent with two distinct coordination environments for the copper(I) atoms—tetrahedral and linear—for the polymer family [(CuCl)(μ‐Cl){Cu(YNC10H14O)}]n. DFT band calculations reveal that the highest energy bands are more localized on the copper(I) tetrahedral sites than on the copper(I) linear sites. The redox properties of [(CuCl)(μ‐Cl){Cu(YNC10H14O)}]n [Y = NMe2 ( 2b ), NH2, and H2NC6H4NC10H14O ( 2a )] studied by cyclic voltammetry show that the oxidation potentials of the two copper centers are in fact indistinguishable. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 |
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| Keywords: | band calculations camphorimine copper DFT metal‐polymer complexes structure synthesis X‐ray X‐ray photoelectron spectroscopy |
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