000117355 001__ 117355
000117355 005__ 20230519145532.0
000117355 0247_ $$2doi$$a10.1039/d1dt01599k
000117355 0248_ $$2sideral$$a126865
000117355 037__ $$aART-2021-126865
000117355 041__ $$aeng
000117355 100__ $$aCaddeo F.
000117355 245__ $$aLuminescent gold-thallium derivatives with a pyridine-containing 12-membered aza-thioether macrocycle
000117355 260__ $$c2021
000117355 5060_ $$aAccess copy available to the general public$$fUnrestricted
000117355 5203_ $$aThe coordination modes of the ligand 2, 5, 8-trithia[9](2, 6)pyridinophane (L) to thallium(i), gold(iii) and gold(i) have been studied. Thallium(i) is coordinated by the macrocyclic ligand in [Tl(L)](PF6) (1) through all the sulfur and nitrogen atoms, in a distorted square-pyramidal geometry with the thallium(i) ion in the apical position and with the presence of an inert lone pair. Gold(iii) is bonded by the ligand only through the nitrogen of the pyridine group in [AuCl3(L)] (2), whereas two AuI-C6F5fragments coordinate the sulfur atoms next to the pyridine moiety of the ligand in [{Au(C6F5)}2(µ-L)] (3), which form a linear polymer through intermolecular aurophilic contacts. The heterometallic TlI/AuIcomplex {[Au(C6F5)2Tl]2(L)}n(4) features a polymeric structural nature with a metallic pseudo-rhombic Au2Tl2core, which repeats itself forming a zig-zag polymer. In each Au2Tl2unit only one thallium atom is bonded by the NS3donor set of the macrocyclic ligand and also forms two unsupported Au-Tl bonds with two [Au(C6F5)2]-units in an overall pseudo-octahedral geometry. The other thallium atom similarly bridges the same [Au(C6F5)2]-units and links a neighbouring Au2Tl2moiety, thus exhibiting a distorted trigonal planar geometry being bonded only to three gold atoms with unsupported Au-Tl interactions. This complex displays an interesting thermochromic behaviour showing emissions mainly resulting from MM'CT transitions at room temperature. At 77 K a dual emission appears, probably arising from the two different thallium environments. DFT calculations have been carried out in the attempt to investigate the origin of the emissions of complex4. © The Royal Society of Chemistry 2021.
000117355 536__ $$9info:eu-repo/grantAgreement/ES/MCIU/PID2019-104379RB-C21$$9info:eu-repo/grantAgreement/ES/MCIU/RTI2018-097836-J-I00$$9info:eu-repo/grantAgreement/ES/MCIU/RYC2018-025872
000117355 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttp://creativecommons.org/licenses/by-nc/3.0/es/
000117355 590__ $$a4.569$$b2021
000117355 592__ $$a0.864$$b2021
000117355 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 46 = 0.152$$c2021$$dQ1$$eT1
000117355 593__ $$aInorganic Chemistry$$c2021$$dQ1
000117355 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000117355 700__ $$0(orcid)0000-0002-1218-7218$$aFernández-Moreira V.$$uUniversidad de Zaragoza
000117355 700__ $$aArca M.
000117355 700__ $$aPintus A.
000117355 700__ $$0(orcid)0000-0003-1984-7538$$aLaguna A.$$uUniversidad de Zaragoza
000117355 700__ $$aLippolis V.
000117355 700__ $$0(orcid)0000-0003-0553-0695$$aGimeno M.C.
000117355 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000117355 773__ $$g50, 28 (2021), 9709-9718$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000117355 8564_ $$s2515807$$uhttps://zaguan.unizar.es/record/117355/files/texto_completo.pdf$$yVersión publicada
000117355 8564_ $$s1617628$$uhttps://zaguan.unizar.es/record/117355/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000117355 909CO $$ooai:zaguan.unizar.es:117355$$particulos$$pdriver
000117355 951__ $$a2023-05-18-15:31:46
000117355 980__ $$aARTICLE