000085398 001__ 85398
000085398 005__ 20200117221620.0
000085398 0247_ $$2doi$$a10.1039/c8dt03833c
000085398 0248_ $$2sideral$$a109588
000085398 037__ $$aART-2018-109588
000085398 041__ $$aeng
000085398 100__ $$aSrinivasan, A.
000085398 245__ $$aTemperature dependence of the spin state and geometry in tricobalt paddlewheel complexes with halide axial ligands
000085398 260__ $$c2018
000085398 5060_ $$aAccess copy available to the general public$$fUnrestricted
000085398 5203_ $$aTrinuclear cobalt paddlewheel complexes, [Co-3(dpa)(4)X-2] (dpa = the anion of 2, 2-dipyridylamine, X = Cl-, Br-, -NCS-, -CN-, (NC)(2)N-), are known to demonstrate a thermally-induced spin-crossover (SCO). Despite a wealth of structural and magnetic information about such complexes, the role of the axial ligand on the characteristic SCO temperature (T-1/2) remains ambiguous. The situation is complicated by the observation that the solid state geometry of the complexes, symmetric or unsymmetric, with respect to the central cobalt ion, also appears to influence the SCO behavior. In order to seek trends in the relationship between the nature of the axial ligand, geometry and magnetic properties, we have prepared the first examples of tricobalt paddlewheel complexes with axial fluorido and iodido ligands, as well as two new chlorido and bromido solvates. Their SCO properties are discussed in the context of an examination of previously reported chlorido and bromido adducts. The main conclusions are: (1) T-1/2 values follow the trend I- < Br- approximate to Cl- < F-; (2) while the molecular geometry is predominantly guided by crystal packing for the Cl-, Br- and I- derivatives, the presence of an axial fluoride may favor a more symmetric core; (3) the magnetic characterization of a second example of an unsymmetric complex supports the observation that they display dramatically lower T-1/2 values than their symmetric analogues; and (4) SCO in crystallographically symmetric compounds apparently occurs without loss of molecular or crystallographic symmetry, while a gradual geometric transformation linking the temperature dependence of quasi-symmetric to unsymmetric in crystallographically unconstrained compounds was found.
000085398 536__ $$9info:eu-repo/grantAgreement/ES/MINECO/MAT2015-68200-C2-1-P$$9info:eu-repo/grantAgreement/EUR/MOLSPIN-COST/CA15128
000085398 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000085398 590__ $$a4.052$$b2018
000085398 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 45 = 0.156$$c2018$$dQ1$$eT1
000085398 592__ $$a1.12$$b2018
000085398 593__ $$aInorganic Chemistry$$c2018$$dQ1
000085398 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000085398 700__ $$aWang, X.P.
000085398 700__ $$aClerac, R.
000085398 700__ $$aRouzieres, M.
000085398 700__ $$0(orcid)0000-0002-0444-996X$$aFalvello, L.R.$$uUniversidad de Zaragoza
000085398 700__ $$aMcGrady, J.E.
000085398 700__ $$aHillard, E.A.
000085398 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000085398 773__ $$g47, 46 (2018), 16798-16806$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000085398 8564_ $$s586803$$uhttps://zaguan.unizar.es/record/85398/files/texto_completo.pdf$$yPostprint
000085398 8564_ $$s508848$$uhttps://zaguan.unizar.es/record/85398/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000085398 909CO $$ooai:zaguan.unizar.es:85398$$particulos$$pdriver
000085398 951__ $$a2020-01-17-21:53:21
000085398 980__ $$aARTICLE