Domain Wall Dynamics in a Ferroelastic Spin Crossover Complex with Giant Magnetoelectric Coupling.

Pinned and mobile ferroelastic domain walls are detected in response to mechanical stress in a Mn3+ complex with two-step thermal switching between the spin triplet and spin quintet forms. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy on [MnIII(3,5-diCl-sal2(323))]BPh4 reveal three distinct symmetry-breaking phase transitions in the polar space group series Cc → Pc → P1 → P1(1/2). The transition mechanisms involve coupling between structural and spin state order parameters, and the three transitions are Landau tricritical, first order, and first order, respectively. The two first-order phase transitions also show changes in magnetic properties and spin state ordering in the Jahn-Teller-active Mn3+ complex. On the basis of the change in symmetry from that of the parent structure, Cc, the triclinic phases are also ferroelastic, which has been confirmed by resonant ultrasound spectroscopy. Measurements of magnetoelectric coupling revealed significant changes in electric polarization at both the Pc → P1 and P1 → P1(1/2) transitions, with opposite signs. All these phases are polar, while P1 is also chiral. Remanent electric polarization was detected when applying a pulsed magnetic field of 60 T in the P1→ P1(1/2) region of bistability at 90 K. Thus, we showcase here a rare example of multifunctionality in a spin crossover material where the strain and polarization tensors and structural and spin state order parameters are strongly coupled.

Modulation of Mn3+ Spin State by Guest Molecule Inclusion.

Spin state preferences for a cationic Mn3+ chelate complex in four different crystal lattices are investigated by crystallography and SQUID magnetometry. The [MnL1]+ complex cation was prepared by complexation of Mn3+ to the Schiff base chelate formed from condensation of 4-methoxysalicylaldehyde and 1,2-bis(3-aminopropylamino)ethane. The cation was crystallized separately with three polyatomic counterions and in one case was found to cocrystallize with a percentage of unreacted 4-methoxysalicylaldehyde starting material. The spin state preferences of the four resultant complexes [MnL1]CF3SO3·xH2O, (1), [MnL1]PF6·xH2O, (2), [MnL1]PF6·xsal·xH2O, (2b), and [MnL1]BPh4, (3), were dependent on their ability to form strong intermolecular interactions. Complexes (1) and (2), which formed hydrogen bonds between [MnL1]+, lattice water and in one case also with counterion, showed an incomplete thermal spin crossover over the temperature range 5-300 K. In contrast, complex (3) with the BPh4-, counterion and no lattice water, was locked into the high spin state over the same temperature range, as was complex (2b), where inclusion of the 4-methoxysalicylaldehyde guest blocked the H-bonding interaction.

Stress-Induced Domain Wall Motion in a Ferroelastic Mn3+ Spin Crossover Complex.

Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry-breaking phase transitions in the mononuclear Mn3+ compound [Mn(3,5-diBr-sal2 (323))]BPh4 , 1. The first at 250 K, involves the space group change Cc→Pc and is thermodynamically continuous, while the second, Pc→P1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress-induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc-P1 transition.

Substituent effects on spin state in a series of mononuclear manganese(III) complexes with hexadentate Schiff-Base ligands.

Eleven new mononuclear manganese(III) complexes prepared from two hexadentate ligands, L1 and L2, with different degrees of steric bulk in the substituents are reported. L1 and L2 are Schiff bases resulting from condensation of N,N'-bis(3-aminopropyl)ethylenediamine with 3-methoxy-2-hydroxybenzaldehyde and 3-ethoxy-2-hydroxybenzaldehyde respectively, and are members of a ligand series we have abbreviated as R-Sal2323 to indicate the 323 alkyl connectivity in the starting tetraamine and the substitution (R) on the phenolate ring. L1 hosts a methoxy substituent on both phenolate rings, while L2 bears a larger ethoxy group in the same position. Structural and magnetic properties are reported in comparison with those of a previously reported analogue with L1, namely, [MnL1]NO3, (1e). The BPh4(-) and PF6(-) complexes [MnL1]BPh4, (1a), [MnL2]BPh4, (2a), [MnL1]PF6, (1b'), and [MnL2]PF6, (2b), with both ligands L1 and L2, remain high-spin (HS) over the measured temperature range. However, the monohydrate of (1b') [MnL1]PF6·H2O, (1b), shows gradual spin-crossover (SCO), as do the ClO4(-), BF4(-), and NO3(-) complexes [MnL1]ClO4·H2O, (1c), [MnL2]ClO4, (2c), [MnL1]BF4·H2O, (1d), [MnL2]BF4·0.4H2O, (2d), [MnL1]NO3, (1e), and [MnL2]NO3·EtOH, (2e). The three complexes formed with ethoxy-substituted ligand L2 all show a higher T1/2 than the analogous complexes with methoxy-substituted ligand L1. Analysis of distortion parameters shows that complexes formed with the bulkier ligand L2 exhibit more deformation from perfect octahedral geometry, leading to a higher T1/2 in the SCO examples, where T1/2 is the temperature where the spin state is 50% high spin and 50% low spin. Spin state assignment in the solid state is shown to be solvate-dependent for complexes (1b) and (2e), and room temperature UV-visible and NMR spectra indicate a solution-state spin assignment intermediate between fully HS and fully low spin in 10 complexes, (1a)-(1e) and (2a)-(2e).