{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,11]],"date-time":"2025-11-11T13:29:58Z","timestamp":1762867798770,"version":"build-2065373602"},"reference-count":68,"publisher":"MDPI AG","issue":"5","license":[{"start":{"date-parts":[[2019,5,7]],"date-time":"2019-05-07T00:00:00Z","timestamp":1557187200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["UID\/QUI\/00100\/2019","PTDC\/QEQ-QIN\/3967\/2014","SFRH\/BPD\/24691\/2005"],"award-info":[{"award-number":["UID\/QUI\/00100\/2019","PTDC\/QEQ-QIN\/3967\/2014","SFRH\/BPD\/24691\/2005"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Catalysts"],"abstract":"<jats:p>Reactions between N6O4 macrocyclic 1,4,19,22,25,40-hexaaza-10,13,31,34-tetraoxa-6,14,27,35(1,4)-tetrabenzenacyclopentacontane (L) and several copper salts (viz. trifuoromethane and toluene sulfonates, nitrate, perchlorate, benzoate, and acetate) led to the formation of dinuclear compounds [Cu2(OSO2CF3)2(DMF)2L](SO3CF3)2 (1), [Cu2(p-OSO2C6H4Me)2L(DMF)2](SO3C6H4Me)2 (2), [Cu2(ONO2)2L(DMF)2](NO3)2 (3), [Cu2(OClO3)2(DMF)2L](ClO4)2 (4), [Cu2(OOCPh)2L(H2O)2](O2CPh)2 (5), and [Cu2(OOCMe)4L] (6), which were characterized by IR, elemental analysis and TG-DTA (thermogravimetric-differential thermal analysis), as well as by single-crystal X-ray diffraction, EPR (electron paramagnetic resonance) spectroscopy, and electrochemical techniques (cyclic voltammetry and controlled potential electrolysis). The molecular structures of compounds 1\u20136 reveal a considerable conformational flexibility of the ligand L, which allowed its readjustment for the formation of the metal compounds and confirmed the presence of dinuclear endo macrocyclic species. In every case, the L ligand coordinates to each copper cation via three nitrogen atoms, with the remaining coordination positions of the metal square pyramid environment being accomplished by neutral or anionic ligands. The macrocyclic cavities appear to be adequate for the enclosure of a neutral species as proved by compound 6 with 1,4-dioxane. The compounds, in combination with the TEMPO (2,2,6,6-tetramethyl-piperidinyloxyl) radical and in alkaline aqueous solution, act as efficient catalysts in the aerobic oxidation of different alcohols to the corresponding aldehydes (yields up to 99% and TON up 232) after 20 h at 70 \u00b0C. In addition, the microwave-assisted solvent-free peroxidative oxidation (by tert-butylhydroperoxide, TBHP) of 1-phenylethanol led to acetophenone yields up to 99% and TOF of 1.1 \u00d7 103 after 0.5 h, without any additive.<\/jats:p>","DOI":"10.3390\/catal9050424","type":"journal-article","created":{"date-parts":[[2019,5,13]],"date-time":"2019-05-13T05:35:39Z","timestamp":1557725739000},"page":"424","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Synthesis and Structure of Copper Complexes of a N6O4 Macrocyclic Ligand and Catalytic Application in Alcohol Oxidation"],"prefix":"10.3390","volume":"9","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1629-7764","authenticated-orcid":false,"given":"Zhen","family":"Ma","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China"},{"name":"Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}]},{"given":"Qijun","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4060-1057","authenticated-orcid":false,"given":"Elisabete","family":"C. B. A. Alegria","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"},{"name":"Chemical Engineering Department, Instituto Superior de Engenharia de Lisboa, Instituto Polit\u00e9cnico de Lisboa, R. Conselheiro Em\u00eddio Navarro, 1959-007 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4836-2409","authenticated-orcid":false,"given":"M. F\u00e1tima","family":"C. Guedes da Silva","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5403-9352","authenticated-orcid":false,"given":"Lu\u00edsa","family":"M. D. R. S. Martins","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1463-1068","authenticated-orcid":false,"given":"Jo\u00e3o P.","family":"Telo","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2208-5183","authenticated-orcid":false,"given":"Isabel","family":"Correia","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8323-888X","authenticated-orcid":false,"given":"Armando","family":"J. L. Pombeiro","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Complexo I, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. 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