{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,11]],"date-time":"2025-11-11T13:27:17Z","timestamp":1762867637018,"version":"build-2065373602"},"reference-count":42,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2018,12,23]],"date-time":"2018-12-23T00:00:00Z","timestamp":1545523200000},"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":["PTDC\/QEQ-ERQ\/1648\/2014","PTDC\/QEQ-QIN\/3967\/2014","UID\/QUI\/00100\/2013"],"award-info":[{"award-number":["PTDC\/QEQ-ERQ\/1648\/2014","PTDC\/QEQ-QIN\/3967\/2014","UID\/QUI\/00100\/2013"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>One-dimensional (1D) polynuclear Cu(II) complex (1) derived from (5-bromo-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H2L) is synthesized and characterized by elemental analysis, IR spectroscopy, ESI-MS, and single crystal X-ray crystallography. Its catalytic performance towards the solvent-free microwave-assisted peroxidative oxidation of aliphatic and aromatic hydrocarbons under mild conditions is compared with that of dinuclear Cu(II) complexes (2 and 3) of the same ligand, previously reported as antiproliferative agents. Polymer 1 exhibits the highest activity, either for the oxidation of cyclohexane (leading to overall yields, based on the alkane, of up to 39% of cyclohexanol and cyclohexanone) or towards the oxidation of toluene (selectively affording benzaldehyde up to a 44% yield), after 2 or 2.5 h of irradiation at 80 or 50 \u00b0C, respectively.<\/jats:p>","DOI":"10.3390\/molecules24010047","type":"journal-article","created":{"date-parts":[[2018,12,24]],"date-time":"2018-12-24T10:37:49Z","timestamp":1545647869000},"page":"47","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":29,"title":["Catalytic Activity of Polynuclear vs. Dinuclear Aroylhydrazone Cu(II) Complexes in Microwave-Assisted Oxidation of Neat Aliphatic and Aromatic Hydrocarbons"],"prefix":"10.3390","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3349-9154","authenticated-orcid":false,"given":"Manas","family":"Sutradhar","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"given":"Tannistha Roy","family":"Barman","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8323-888X","authenticated-orcid":false,"given":"Armando J. L.","family":"Pombeiro","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5403-9352","authenticated-orcid":false,"given":"Lu\u00edsa M.D.R.S.","family":"Martins","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2018,12,23]]},"reference":[{"key":"ref_1","first-page":"41","article-title":"Fibers, 4 Polyamide Fibers","volume":"Volume 11","author":"Estes","year":"2011","journal-title":"Ullmann\u2019s Encyclopedia of Industrial Chemistry"},{"key":"ref_2","unstructured":"Ahmed, J., Ahuja, S., Ali, I., Anderson, C., Anderson, M.J., Arai, Y., Braglia, M., Babirad, S., Bag, D., and Bagchi, A. (2014). Kirk-Othmer Encyclopedia of Chemical Technology, Wiley & Sons."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Chiusoli, G.P., and Maitlis, P.M. (2006). Metal-Catalysis in Industrial Organic Processes, Royal Society of Chemistry.","DOI":"10.1039\/9781847555328"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"74","DOI":"10.1016\/j.ccr.2014.01.013","article-title":"Tris(pyrazol-1yl)methane metal complexes for catalytic mild oxidative functionalizations of alkanes, alkenes and ketones","volume":"265","author":"Martins","year":"2014","journal-title":"Coord. Chem. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2236","DOI":"10.1002\/ejic.201600053","article-title":"Water-soluble C-scorpionate complexes: Catalytic and biological applications","volume":"15\u201316","author":"Martins","year":"2016","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"200","DOI":"10.1016\/j.ccr.2015.01.020","article-title":"Vanadium complexes: Recent progress in oxidation catalysis","volume":"301\u2013302","author":"Sutradhar","year":"2015","journal-title":"Coord. Chem. Rev."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Shul\u2019pin, G.B. (2016). New trends in oxidative functionalization of carbon\u2013hydrogen bonds: A review. Catalysts, 6.","DOI":"10.3390\/catal6040050"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"8733","DOI":"10.1039\/c1dt10339c","article-title":"Cleavage of unreactive bonds with pincer metal complexes","volume":"40","author":"Albrecht","year":"2011","journal-title":"Dalton Trans."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2456","DOI":"10.1021\/cs3005083","article-title":"Coordination versatility of sp3-Hybridized pincer ligands toward ligand\u2014Metal cooperative catalysis","volume":"2","author":"Gelman","year":"2012","journal-title":"ACS Catal."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1802","DOI":"10.1021\/acscatal.7b03454","article-title":"Cu2+ or Fe3+ terpyridine\/aptamer conjugates: Nucleoapzymes catalyzing the oxidation of dopamine to aminochrome","volume":"8","author":"Biniuri","year":"2018","journal-title":"ACS Catal."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"15026","DOI":"10.1021\/acs.inorgchem.7b02320","article-title":"Si10Cu6N4 cage hexacoppersilsesquioxanes containing N ligands: Synthesis, structure, and high catalytic activity in peroxide oxidations","volume":"56","author":"Kulakova","year":"2017","journal-title":"Inorg. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1806","DOI":"10.1016\/j.ccr.2013.01.027","article-title":"Metal complexes with heteroscorpionate ligands based on the bis(pyrazol-1-yl)methane moiety: Catalytic chemistry","volume":"257","author":"Otero","year":"2013","journal-title":"Coord. Chem. Rev."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"2446","DOI":"10.1021\/cs300404u","article-title":"Transition metal versus heavy metal synergy in selective catalytic oxidations","volume":"2","author":"Potter","year":"2012","journal-title":"ACS Catal."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"776","DOI":"10.1016\/j.ccr.2012.10.006","article-title":"Metallated cavitands (calixarenes, resorcinarenes, cyclodextrins) with internal coordination sites","volume":"257","author":"Armspach","year":"2013","journal-title":"Coord. Chem. Rev."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"5262","DOI":"10.1039\/c2cs35047e","article-title":"Catalysis by metal nanoparticles embedded on metal-organic frameworks","volume":"41","author":"Dhakshinamoorthy","year":"2012","journal-title":"Chem. Soc. Rev."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"4048","DOI":"10.1016\/j.catcom.2014.01.024","article-title":"Microwave-assisted and solvent-free peroxidative oxidation of 1-phenylethanol to acetophenone with a Cu(II)-TEMPO catalytic system","volume":"48","author":"Sabbatini","year":"2014","journal-title":"Catal. Commun."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"706","DOI":"10.1002\/adsc.200700529","article-title":"Scorpionate vanadium, iron and copper complexes as selective catalysts for the peroxidative oxidation of cyclohexane under mild conditions","volume":"350","author":"Silva","year":"2008","journal-title":"Adv. Synth. Catal."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"758","DOI":"10.1016\/j.crci.2015.03.018","article-title":"Catalytic oxidation of cyclohexane with hydrogen peroxide and a tetracopper(II) complex in an ionic liquid","volume":"18","author":"Ribeiro","year":"2015","journal-title":"Rendus Rendu Chim."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"19203","DOI":"10.3390\/molecules201019203","article-title":"Greener selective cycloalkane oxidation with hydrogen peroxide catalyzed by copper-5-(4-pyridyl)tetrazolate metal-organic frameworks","volume":"20","author":"Martins","year":"2015","journal-title":"Molecules"},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Sutradhar, M., Martins, L.M.D.R.S., Guedes da Silva, M.F.C., Liu, C.-M., and Pombeiro, A.J.L. (2015). Trinuclear Cu(II) structural isomers: Coordination, magnetism, electrochemistry and catalytic activity toward oxidation of alkanes. Eur. J. Inorg. Chem., 3959\u20133969.","DOI":"10.1002\/ejic.201500440"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"2303","DOI":"10.1021\/acs.cgd.5b00083","article-title":"Novel coordination polymers with (pyrazolato)-based tectons: Catalytic activity in the peroxidative oxidation of alcohols and cyclohexane","volume":"15","author":"Timokhin","year":"2015","journal-title":"Cryst. Growth Des."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"9946","DOI":"10.1021\/ic501704g","article-title":"Cooperative Metal-Ligand Assisted E\/Z Isomerisation and Cyano-groups Activation at CuII and CoII Complexes of Arylhydrazones of Active Methylene Nitriles","volume":"53","author":"Mahmudov","year":"2014","journal-title":"Inorg. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","unstructured":"Sutradhar, M., Alegria, E.C.B.A., Guedes da Silva, M.F.C., Martins, L.M.D.R.S., and Pombeiro, A.J.L. (2016). Aroylhydrazone Cu(II) complexes in keto form: Structural characterization and catalytic activity towards cyclohexane oxidation. Molecules, 21.","DOI":"10.3390\/molecules21040425"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"168","DOI":"10.1021\/acs.organomet.7b00845","article-title":"Mild and regioselective hydroxylation of methyl group in neocuproine: Approach to an N,O-ligated Cu6 cage phenylsilsesquioxane","volume":"37","author":"Bilyachenko","year":"2018","journal-title":"Organometallics"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"6234","DOI":"10.1021\/cr300527g","article-title":"Aerobic copper-catalyzed organic reactions","volume":"113","author":"Allen","year":"2013","journal-title":"Chem. Rev."},{"key":"ref_26","first-page":"14270","article-title":"Partial oxidation of toluene in CH3COOH by H2O2 in the presence of VO(acac)2 catalyst","volume":"113","author":"Wang","year":"2009","journal-title":"J. Phys. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1016\/bs.adomc.2015.02.004","article-title":"Catalytic oxidation of alcohols: Recent advances","volume":"63","author":"Kopylovich","year":"2015","journal-title":"Adv. Organomet. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","unstructured":"Horikoshi, S., and Serpone, N. (2015). Microwaves in Catalysis: Methodology and Applications, John Wiley & Sons.","DOI":"10.1002\/9783527688111"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1016\/j.apcata.2015.01.005","article-title":"Oxido vanadium complexes with tridentate aroylhydrazone as catalyst precursors for solvent-free microwave-assisted oxidation of alcohol","volume":"493","author":"Sutradhar","year":"2015","journal-title":"Appl. Catal. A Gen."},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Alexandru, M., Cazacu, M., Arvinte, A., Shova, S., Turta, C., Simionescu, B.C., Dobrov, A., Alegria, E.C.B.A., Martins, L.M.D.R.S., and Pombeiro, A.J.L. (2014). m-Chlorido-bridged dimanganese(II) complexes of the Schiff base derived from [2+2]condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: Structure, magnetism, electrochemical behaviour and catalytic oxidation of secondary alcohols. Eur. J. Inorg. Chem., 120\u2013131.","DOI":"10.1002\/ejic.201300969"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1837","DOI":"10.1021\/acs.cgd.5b01178","article-title":"Metal\u2013organic frameworks with pyridyl-based isophthalic acid and their catalytic applications in microwave assisted peroxidative oxidation of alcohols and Henry reaction","volume":"16","author":"Karmakar","year":"2016","journal-title":"Cryst. Growth Des."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1016\/j.jinorgbio.2017.07.034","article-title":"Mixed ligand aroylhydrazone and N-donor heterocyclic Lewis base Cu(II) complexes as potential antiproliferative agents","volume":"175","author":"Sutradhar","year":"2017","journal-title":"J. Inorg. Biochem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"224","DOI":"10.1016\/j.mcat.2017.07.006","article-title":"Microwave-assisted peroxidative oxidation of toluene and 1-phenylethanol with monomeric keto and polymeric enol aroylhydrazone Cu(II) complexes","volume":"439","author":"Sutradhar","year":"2017","journal-title":"Mol. Catal."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"764","DOI":"10.1002\/poc.1824","article-title":"Trends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-diones","volume":"24","author":"Kopylovich","year":"2011","journal-title":"J. Phys. Org. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"567","DOI":"10.1126\/science.172.3983.567","article-title":"Quadratic elongation: A quantitative measure of distortion in coordination polyhedral","volume":"172","author":"Robinson","year":"1971","journal-title":"Science"},{"key":"ref_36","doi-asserted-by":"crossref","unstructured":"Addison, A.W., Rao, T.N., Reedijk, J., van Rijn, J., and Verschoor, G.C. (1984). Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen\u2013sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2\u2032-yl)-2,6-dithiaheptane]copper(II) perchlorate. J. Chem. Soc. Dalton Trans., 1349\u20131356.","DOI":"10.1039\/DT9840001349"},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Maharramov, A.M., Mahmudov, K.T., Kopylovich, M.N., and Pombeiro, A.J.L. (2016). Non-Covalent Interactions in the Synthesis and Design of New Compounds, John Wiley & Sons, Inc.","DOI":"10.1002\/9781119113874"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1007\/BF02070104","article-title":"Formation of alkyl peroxides in oxidation of alkanes by H2O2 catalyzed by transition metal complexes","volume":"48","author":"Nizova","year":"1992","journal-title":"React. Kinet. Catal. Lett."},{"key":"ref_39","unstructured":"Bruker, S. (2004). APEX2 & SAINT, AXS Inc."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"115","DOI":"10.1107\/S0021889898007717","article-title":"SIR97: A new tool for crystal structure determination and refinement","volume":"32","author":"Altomare","year":"1999","journal-title":"J. Appl. Crystallogr."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1107\/S0108767307043930","article-title":"A short history of SHELX","volume":"64","author":"Sheldrick","year":"2008","journal-title":"Acta Crystallogr. A"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"849","DOI":"10.1107\/S0021889812029111","article-title":"WinGX and ORTEP for Windows: An update","volume":"45","author":"Farrugia","year":"2012","journal-title":"J. Appl. Cryst."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/1\/47\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T15:35:47Z","timestamp":1760196947000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/1\/47"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,12,23]]},"references-count":42,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2019,1]]}},"alternative-id":["molecules24010047"],"URL":"https:\/\/doi.org\/10.3390\/molecules24010047","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2018,12,23]]}}}