Efficient synthetic route to heterobimetallic trinuclear complexes [Ln–Mn–Ln] and their single molecule magnetic properties

Abstract

A series of mononuclear lanthanoidate complexes isolated as [Bu4N][Ln(QCl4)] 1Ln (QCl = 5-chloro-8-quinolinolate; Ln = Eu, Gd, Tb, Dy, Ho, and Er) have been prepared, characterised, and used as facile...

Structure and assembly studies of two planar Dy(iii) single molecule magnets with double relaxations

“…As is well known, four possible relaxation processes might involve in the relaxation of Dy( iii ) SMMs, which are the Orbach process ( τ 0 −1 exp(− U eff / k B T )), the Raman process ( CT n ), the direct relaxation process (A H m T ) and the QTM processes ( τ QTM −1 ). 66–68 Thus, the ln( τ / s ) versus T −1 plots of 1 and 2 were simulated based on eqn (1) as shown in Fig. 4c, d, g and h, giving parameters τ 0 = 5.17(2) × 10 −6 s, U eff / k B = 21.20(4) K, C = −2.4(1) s −1 K − n , n = 4.14(2), τ QTM −1 = 2.836(5) × 10 3 s −1 and A H m = 81.6(3) (FR of 1 ) and τ 0 = 1.5(9) × 10 −5 s, U eff / k B = 33.6(5) K, C = −0.003(2) s −1 K − n , n = 6.2(4), τ QTM −1 = 59(6) s −1 and A H m = 255.8(5) (SR of 1 ); τ 0 = 1.56(1) × 10 −6 s, U eff / k B = 13.37(2) K, C = 0.079(6) s −1 K − n , n = 7.6(4), τ QTM −1 = 1.37(2) × 10 3 s −1 and A H m = −105(13) (FR of 2 ) and τ 0 = 1.2(3) × 10 −7 s, U eff / k B = 72(1) K, C = 0.24(1) s −1 K − n , n = 3.13(3), τ QTM −1 = 19.0(1) s −1 and A H m = 0.43(9) (SR of 2 ).…”

“…As is well known, four possible relaxation processes might involve in the relaxation of Dy(III) SMMs, which are the Orbach process (t 0 À1 exp(ÀU eff /k B T)), the Raman process (CT n ), the direct relaxation process (AH m T) and the QTM processes (t QTM À1 ). [66][67][68] Thus, the ln(t/s) versus T À1 plots of 1 and 2 were simulated based on eqn (1) as shown in Fig. 4c, d, g and h, giving parameters t 0 = 5.17…”

Slow Magnetic Relaxation of Linear Trinuclear M(II)–Gd(III)–M(II) Complexes with D3 Point Group Symmetry (M(II) = Zn(II) and Mg(II))

“…Linear trinuclear complexes were synthesized using mononuclear complexes using as ligands. , Herein, trinuclear complexes of [Gd­(ZnL) 2 ]­CF 3 SO 3 ·0.5H 2 O ( 1 ), [Y 0.95 Gd 0.05 (ZnL) 2 ]­CF 3 SO 3 ·0.5H 2 O ( 1′ ), and [Gd­(MgL) 2 ]­CF 3 SO 3 ·0.5H 2 O ( 2 ), were synthesized via the reaction of lanthanide triflate and mono-nuclear complexes [Zn­(HL)] (for 1 and 1′ ) or [Mg­(HL)] (for 2 ) at a 1:2 ratio under basic conditions. During complex formation, the Zn­(II) and Mg­(II) complexes behave as tri-dentate oxygen donor ligands toward Gd­(III) or Y­(III) after removal of the phenolic proton under basic conditions.…”

Stability and Solution Behavior of [(dpp-Bian)Ln] and [(dpp-Bian)LnX] (Ln = Yb, Tm, or Dy; X = I, F, or N3)

“…For example, they allowed multielectron transfer reactions for trivalent atoms, , bond formation reactions, and C–H bond activation . Lanthanide atoms complexated with redox-active ligands exhibited a number of interesting magnetic properties, − e.g., those of an exchange-coupled lanthanide radical single-molecular magnet and luminescent and electrochemical properties. − That allowed them to be employed as switchable materials, biosensors, − catalysts for controlled copolymerization, and agents for rare-earth element separations …”