Molecular-scale dynamics of light-induced spin cross-over in a two-dimensional layer.

Spin cross-over molecules show the unique ability to switch between two spin states when submitted to external stimuli such as temperature, light or voltage. If controlled at the molecular scale, such switches would be of great interest for the development of genuine molecular devices in spintronics, sensing and for nanomechanics. Unfortunately, up to now, little is known on the behaviour of spin cross-over molecules organized in two dimensions and their ability to show cooperative transformation. Here we demonstrate that a combination of scanning tunnelling microscopy measurements and ab initio calculations allows discriminating unambiguously between both states by local vibrational spectroscopy. We also show that a single layer of spin cross-over molecules in contact with a metallic surface displays light-induced collective processes between two ordered mixed spin-state phases with two distinct timescale dynamics. These results open a way to molecular scale control of two-dimensional spin cross-over layers.

Fe(II)(pap-5NO2)2 and Fe(II)(qsal-5NO2)2 Schiff-base spin-crossover complexes: a rare example with photomagnetism and room-temperature bistability.

We focus here on the properties of Fe complexes formed with Schiff bases involved in the chemistry of Fe(III) spin-transition archetypes. The neutral Fe(pap-5NO2)2 (1) and Fe(qsal-5NO2)2·Solv (2 and 2·Solv) compounds (Solv = 2H2O) derive from the reaction of Fe(II) salts with the condensation products of pyridine-2-carbaldehyde with 2-hydroxy-5-nitroaniline (Hpap-5NO2) or 5-nitrosalicylaldehyde with quinolin-8-amine (Hqsal-5NO2), respectively. While the Fe(qsal-5NO2)2·Solv solid is essentially low spin (S = 0) and requires temperatures above 300 K to undergo a S = 0 ↔ S = 2 spin-state switching, the Fe(pap-5NO2)2 one presents a strongly cooperative first-order transition (T↓ = 291 K, T↑ = 308 K) centered at room temperature associated with a photomagnetic effect at 10 K (TLIESST = 58 K). The investigation of these magnetic behaviors was conducted with single-crystal X-ray diffraction (1, 100 and 320 K; 2, 100 K), Mössbauer, IR, UV-vis (1 and 2·Solv), and differential scanning calorimetry (1) measurements. The Mössbauer analysis supports a description of these compounds as Fe(II) Schiff-base complexes and the occurrence of a metal-centered spin crossover process. In comparison with Fe(III) analogues, it appears that an expanded coordination sphere stabilizes the valence 2+ state of the Fe ion in both complexes. Strong hydrogen-bonding interactions that implicate the phenolato group bound to Fe(II) promote the required extra-stabilization of the S = 2 state and thus determines the spin transition of 1 centered at room temperature. In the lattice, the hydrogen-bonded sites form infinite chains interconnected via a three-dimensional network of intermolecular van der Waals contacts and π-π interactions. Therefore, the spin transition of 1 involves the synergetic influence of electrostatic and elastic interactions, which cause the enhancement of cooperativity and result in the bistability at room temperature.

Lanthanide triangles sandwiched by tetranuclear copper complexes afford a family of hendecanuclear heterometallic complexes [Ln(III)3Cu(II)8] (Ln = La-Lu): synthesis and magnetostructural studies.

Reaction in ethanol of 3-hydroxymethylen-5-methylsalicylaldoxime (H3L) with CuCl2·2H2O and LnCl3·xH2O [Ln = La (1), Ce (2), Pr (3), Nd (4), Eu (5), Gd (6), Tb (7), Dy (8), Er (9), Yb (10), Lu (11), Ho (12)] allowed the synthesis of a family of hendecanuclear heterometallic copper(II)-lanthanide(III) clusters with general formula [Ln(III)3Cu(II)8(HL)6(µ4-O)2Cl6(H2O)8]Cl3 (1-12). According to the single-crystal X-ray diffraction investigation, the complexes are isomorphous and crystallize in the trigonal R32 group. The hendecanuclear cluster is formed by two tetrahedral µ4-oxo {Cu4} clusters assembled by three lanthanide ions sandwiched in between. Along the family, the separation between the {Cu4} moieties increases linearly from Lu to La in good correlation with ionic radius of the lanthanide ions. A comparative analysis of the magnetic data for the lanthanum (1) and lutetium (11) compounds shows the presence of ferromagnetic and antiferromagnetic interactions within the µ4-oxo {Cu4} moieties. For the gadolinium (6) and terbium (7) compounds, the magnetic interactions between the lanthanide and the copper ions are found to be ferromagnetic. The dysprosium (8) compound exhibits single-molecule magnet behavior.

Versatile chemical transformations of benzoxazole based ligands on complexation with 3d-metal ions.

Two benzoxazoles derivative ligands were synthesized from the condensation of 3,5-di-tert-butyl-o-benzoquinone (DTBBQ) with ethanolamine or 1,3-diamino-2-hydroxypropane in methanol. Condensation of DTBBQ with ethanolamine gives the expected 5,7-di-tert-butyl-2-methylenhydroxylbenzoxazole (HL1) while with 1,3-diamino-2-hydroxypropane it gives (2-hydroxyethyl-2-{2,4-bis(1,1-dimethylethyl)-1-phenol-6 amino}-2{5,7-di-tert-butyl-benzoxazole}) (H(2)L2) with only one benzoxazole ring instead of the symmetric bis-benzoxazole derivative. The structure of HL1 and H(2)L2 were confirmed by NMR-spectroscopy and X-ray diffraction on a single crystal for HL1. The reaction of HL1 with CuCl(2) gives a mononuclear [Cu(II)(HL1)(2)Cl(2)] (1) complex for which the crystal structure shows that HL1 is preserved. In contrast, upon reaction with nickel(II), cobalt(II), and manganese(II) H(2)L2 is further oxidized and transformed in new ligands HL3 in mononuclear complexes [M(II)(L3)(2)] (M = Ni(II) (2); M = Co(II) (3)) and H(2)L4 in tetranuclear complex [Mn(II)(4)(HL4)(4)Cl(4)] (4) as found from the crystal structures of complexes 2-4. Electrochemical studies for complexes 2 and 3 evidence complicated redox properties. [Mn(II)(4)(HL4)(4)Cl(4)] (4) has a cubane-like structure with a "4 + 2" fashion The magnetic susceptibility of 4 is well fitted considering one Mn---Mn interaction J(a)(Mn(II)-Mn(II)) = -0.50(1) cm(-1) with g = 2.00(7).

Benzoxazole-based heterometallic dodecanuclear complex [Dy(III)4Cu(II)8] with single-molecule-magnet behavior.

Three Cu-Ln (Ln = Dy, Gd, Y) dodecanuclear clusters assembled by a novel ligand of the benzoxazole type are reported. The dysprosium cluster exhibits a frequency dependence of the alternating-current susceptibility and hysteresis loop at low temperature, indicating single-molecule-magnet behavior.