000118980 001__ 118980 000118980 005__ 20240319081013.0 000118980 0247_ $$2doi$$a10.1016/j.solidstatesciences.2022.106959 000118980 0248_ $$2sideral$$a130167 000118980 037__ $$aART-2022-130167 000118980 041__ $$aeng 000118980 100__ $$aSterbinská, Slavomíra 000118980 245__ $$aTemperature-dependent dimerization of TCNQ anion-radical in [Ni (bpy)(3)](2)(TCNQ-TCNQ)(TCNQ)(2)center dot 6H(2)O: Single-crystal structure, magnetic and quantum chemical study 000118980 260__ $$c2022 000118980 5060_ $$aAccess copy available to the general public$$fUnrestricted 000118980 5203_ $$aThe crystal structure of Ni(bpy)(3)](2)(TCNQ-TCNQ)(TCNQ)(2)center dot 6H(2)O (1) was studied by X-ray single-crystal structure analysis at 145 K and 100 K. The crystal structures of 1 at these two temperatures are essentially the same as the crystal structure studied previously at 200 K: the structure is built up of Ni(bpy)(3)](2+) complex cations, two centrosymmetric crystallographically independent TCNQ(center dot-) anion-radicals, disordered sigma- and pi-dimerized (TCNQ)(2) units, and water molecules of crystallization. Lowering the temperature from 200 K, via 145 K-100 K has shown that at lower temperatures the proportions of sigma- and pi-dimerization in the disordered (TCNQ)(2) unit are shifted in favor of sigma-dimerization; moreover, variation of the weaker C-C sigma-bond formed upon dimerization was observed. In addition, lowering the temperature led to a shortening of the distance between the two crystallographically independent anion-radicals which are stacked along the b-axis with overlapped exo groups. The sigma- and pi-dimerization in the disordered (TCNQ)(2) unit was studied by quantum chemical calculations which showed smallest energy difference for sigma and pi-dimer at 200 K with respect to 145 K and 100 K in line with a lowest proportion of the dimerization observed experimentally. Temperature-dependent (1.8-270 K) magnetic study of 1 has shown the contribution of Ni(II) ions (S = 1) and the contribution of four S = 1/2 species carried by TCNQ radicals at higher temperatures, strongly coupled by antiferromagnetic (AFM) exchange interaction at 270 K while at low temperature a negligible contribution of TNCQ radical spins was observed. 000118980 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E11-20R$$9info:eu-repo/grantAgreement/ES/MCINN-FEDER/PGC2018-093451-B-I00 000118980 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/ 000118980 590__ $$a3.5$$b2022 000118980 592__ $$a0.594$$b2022 000118980 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b12 / 42 = 0.286$$c2022$$dQ2$$eT1 000118980 593__ $$aChemistry (miscellaneous)$$c2022$$dQ2 000118980 591__ $$aPHYSICS, CONDENSED MATTER$$b27 / 67 = 0.403$$c2022$$dQ2$$eT2 000118980 593__ $$aMaterials Science (miscellaneous)$$c2022$$dQ2 000118980 591__ $$aCHEMISTRY, PHYSICAL$$b81 / 161 = 0.503$$c2022$$dQ3$$eT2 000118980 593__ $$aCondensed Matter Physics$$c2022$$dQ2 000118980 594__ $$a6.7$$b2022 000118980 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000118980 700__ $$aHolub, Mariia 000118980 700__ $$aHegedüs, Michal 000118980 700__ $$aTitis, Ján 000118980 700__ $$aCizmár, Erik 000118980 700__ $$0(orcid)0000-0002-0444-996X$$aFalvello, Larry R.$$uUniversidad de Zaragoza 000118980 700__ $$aCernák, Juraj 000118980 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000118980 773__ $$g131 (2022), 106959 [8 pp.]$$pSolid state sci.$$tSOLID STATE SCIENCES$$x1293-2558 000118980 8564_ $$s2337970$$uhttps://zaguan.unizar.es/record/118980/files/texto_completo.pdf$$yVersión publicada 000118980 8564_ $$s2452274$$uhttps://zaguan.unizar.es/record/118980/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000118980 909CO $$ooai:zaguan.unizar.es:118980$$particulos$$pdriver 000118980 951__ $$a2024-03-18-15:18:20 000118980 980__ $$aARTICLE