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Influence of supramolecular bonding contacts on the spin crossover behaviour of iron(II) complexes from 2,2′-dipyridylamino/s-triazine ligands

AuthorsRoubeau, Olivier; Teat, Simon J.; Gamez, Patrick
Issue Date2013
PublisherRoyal Society of Chemistry (UK)
CitationDalton Transactions 42(19): 7120-7130 (2013)
AbstractReactions of the related ligands 2-(N,N-bis(2-pyridyl)amino)-4,6- bis(phenoxy)-(1,3,5)triazine (L1) and 2-(N,N-bis(2-pyridyl)amino)-4,6- bis(pentafluorophenoxy)-(1,3,5)triazine (L1F) with iron(ii) thiocyanate produced two spin-crossover coordination compounds with distinct cooperative behaviours. trans-[Fe(L1)2(NCS)2] ·2CH2Cl2 (1) displays a very gradual transition centred at T = 233 K, characterized by a ΔT80 (namely the temperature range within which 80% of the transition considered occurs) of 90 K, while that of fluorinated trans-[Fe(L1F)2(NCS) 2]·2CH3CN (3) is significantly more abrupt (and centred at T = 238 K), with a ΔT80 of 50 K, resulting from supramolecular contacts induced by the fluorinated phenol groups. The coordination compound equivalent to 1 with selenocyanate anions, namely trans-[Fe(L1)2(NCSe)2]·4CH2Cl 2·4CH3OH (2), also exhibits SCO properties centred at T = 238 K, but the transition is very gradual (ΔT80 = 150 K). Light-induced excited spin-state trapping (LIESST) is effective although incomplete for 2 and 3, while it is complete with a TLIESST of 58 K for 1. © The Royal Society of Chemistry 2013.
Identifiersdoi: 10.1039/C3DT50326G
issn: 1477-9226
e-issn: 1477-9234
Appears in Collections:(ICMA) Artículos
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