000048657 001__ 48657 000048657 005__ 20200221144314.0 000048657 0247_ $$2doi$$a10.1039/c5sc03298a 000048657 0248_ $$2sideral$$a94622 000048657 037__ $$aART-2016-94622 000048657 041__ $$aeng 000048657 100__ $$aDíaz-Torres, R. 000048657 245__ $$aMultiscale study of mononuclear CoII SMMs based on curcuminoid ligands 000048657 260__ $$c2016 000048657 5060_ $$aAccess copy available to the general public$$fUnrestricted 000048657 5203_ $$aThis work introduces a novel family of CoII species having a curcuminoid (CCMoid) ligand, 9Accm, attached, namely Co(9Accm)2(py)2] (1) and Co(9Accm)2(2,2'-bpy)] (2), achieved in high yields by the use of a microwave reactor, and exhibiting two different arrangements for the 9Accm ligands, described as "cis"(2) and "trans"(1). The study of the similarities/differences of the magnetic, luminescent and surface behaviors of the two new species, 1 and 2, is the main objective of the present work. The determined single-crystal structures of both compounds are the only CoII-CCMoid structures described in the literature so far. Both compounds exhibit large positive D values, that of 1 (D = +74 cm-1) being three times larger than that of 2 (D = +24 cm-1), and behave as mononuclear Single-Molecule Magnets (SMMs) in the presence of an external magnetic field. Their similar structures but different anisotropy and SMM characteristics provide, for the first time, deep insight on the spin-orbital effects thanks to the use of CASSCF/NEVPT2 calculations implementing such contributions. Further magnetic studies were performed in solution by means of paramagnetic 1H NMR, where both compounds (1 and 2) are stable in CDCl3 and display high symmetry. Paramagnetic NMR appears to be a useful diagnostic tool for the identification of such molecules in solution, where the resonance values found for the methine group (-CH-) of 9Accm vary significantly depending on the cis or trans disposition of the ligands. Fluorescence studies show that both systems display chelation enhancement of quenching (CHEQ) with regard to the free ligand, while 1 and 2 display similar quantum yields. Deposition of 1-2 on HOPG and Si(100) surfaces using spin-coating was studied using AFM; UV photoemission experiments under the same conditions display 2 as the most robust system. The measured occupied density of states of 2 with UV photoemission is in excellent agreement with theoretical DFT calculations. 000048657 536__ $$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-23862-C02-01$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2012-32247$$9info:eu-repo/grantAgreement/ES/MINECO/MAT2012-38319-C02$$9info:eu-repo/grantAgreement/ES/MINECO/MAT2013-47869-C4-2-P 000048657 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/ 000048657 590__ $$a8.668$$b2016 000048657 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b17 / 166 = 0.102$$c2016$$dQ1$$eT1 000048657 592__ $$a4.516$$b2016 000048657 593__ $$aChemistry (miscellaneous)$$c2016$$dQ1 000048657 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000048657 700__ $$aMenelaou, M. 000048657 700__ $$0(orcid)0000-0003-2095-5843$$aRoubeau, O.$$uUniversidad de Zaragoza 000048657 700__ $$aSorrenti, A. 000048657 700__ $$aBrandariz-De-Pedro, G. 000048657 700__ $$aSañudo, E.C. 000048657 700__ $$aTeat, S.J. 000048657 700__ $$aFraxedas, J. 000048657 700__ $$aRuiz, E. 000048657 700__ $$aAliaga-Alcalde, N. 000048657 7102_ $$12003$$2395$$aUniversidad de Zaragoza$$bDpto. Física Materia Condensa.$$cÁrea Física Materia Condensada 000048657 773__ $$g7, 4 (2016), 2793-2803$$pChem. sci.$$tCHEMICAL SCIENCE$$x2041-6520 000048657 8564_ $$s1336470$$uhttps://zaguan.unizar.es/record/48657/files/texto_completo.pdf$$yVersión publicada 000048657 8564_ $$s110784$$uhttps://zaguan.unizar.es/record/48657/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000048657 909CO $$ooai:zaguan.unizar.es:48657$$particulos$$pdriver 000048657 951__ $$a2020-02-21-13:38:49 000048657 980__ $$aARTICLE