RESUMO
We report the synthesis and structures of three luminescent dysprosium(iii) complexes based on fluorinated alkoxide ligands of formulas [Dy(L1)2(THF)4][BPh4]·0.5THF (1), [Dy(L2)2(THF)5][BPh4]·2.5THF (2) and [Dy(L3)2(THF)5][BPh4]·2THF (3) (L1 = (CF3)3CO-, L2 = C6F5C6F4O-, L3 = C6F5C(CH3)O-). Despite the different dysprosium ion geometries (octahedral vs. distorted pentagonal bipyramidal), these systems exhibit a single-molecule magnet (SMM) behavior, but with distinct relaxation dynamics. Moreover, a typical dysprosium-based luminescence is observed for the three complexes, which make them bifunctional magneto-luminescent SMMs. Remarkably, complex 3 exhibits a high anisotropy barrier of 1469 cm-1 and a blocking temperature of 22 K, making it one of the most performant alkoxide-based SMMs with the highest blocking temperature for a luminescent SMM.
RESUMO
A series of new tridentate amidines 2-[Ph2P[double bond, length as m-dash]X]C6H4NHC(tBu)[double bond, length as m-dash]N(2,6-R2C6H3) (X = O, R = iPr (1); X = S, R = Me (2); X = NPh, R = Me (3); X = N(2,6-Me2C6H3), R = Me (4)) bearing various types of donor Ph2P[double bond, length as m-dash]X groups in a pendant chain was synthesized. Bis(alkyl) complexes {2-[Ph2P[double bond, length as m-dash]X]C6H4NC(tBu)N(2,6-R2C6H3)}Ln(CH2SiMe3)2 (Ln = Y, X = O, R = iPr (5); Ln = Er, X = O, R = iPr (6); Ln = Lu, X = O, R = iPr (7); Ln = Y, X = NPh, R = Me (8); Ln = Lu, X = NPh, R = Me (9); Ln = Lu, X = N(2,6-Me2C6H3), R = Me (10)) were prepared using alkane elimination reactions of 1, 3 and 4 with Ln(CH2SiMe3)3(THF)2 (Ln = Y, Er, Lu) in toluene and were isolated in 45 (5), 62 (6), 56 (7), 65 (8), 60 (9), and 60 (10) % yields respectively. The X-ray diffraction studies showed that complexes 6-8 are solvent free and feature intramolecular coordination of the P[double bond, length as m-dash]X (X = O, NPh) group to the lanthanide ions. The ternary systems 5-10/borate/AlR3 (borate = [PhNHMe2][B(C6F5)4], [Ph3C][B(C6F5)4], AlR3 = AliBu3, AliBu2H; molar ratio = 1/1/10 or 1/1/1, toluene) proved to be active in isoprene polymerization and enable complete conversion of 1000-10 000 equivalents of the monomer into a polymer at 25 °C within 0.5-24 h affording polyisoprenes with polydispersities Mw/Mn = 1.22-3.18. A comparative study of the catalytic performance of the bis(alkyl) complexes coordinated by tridentate amidinate ligands containing different pendant donor groups demonstrated that replacement of the Ph2P[double bond, length as m-dash]O group by Ph2P[double bond, length as m-dash]NPh leads to a switch of stereoselectivity in isoprene polymerization from cis-1,4 (up to 98.5%) to trans-1,4 (up to 84.8%). And conversely introduction of methyl substituents in the 2,6 positions of the phenyl group of the Ph2P[double bond, length as m-dash]NPh fragment allows us to restore the 1,4-cis stereoselectivity of the catalytic systems based on bis(alkyl) complex 10 (up to 86.4%).
