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Using Na-encapsulated benzo[18]crown-6 (Na)(B18C6) as a counter cation, we successfully magnetically isolated a fluoride-bridging Dy dinuclear complex {[(PW11O39)Dy(H2O)(2)](2)F} (Dy2POM) with lacunary Keggin ligands. (Na)(B18C6) formed two types of tetramers through C-HMIDLINE HORIZONTAL ELLIPSISO, pi MIDLINE HORIZONTAL ELLIPSIS pi and C-HMIDLINE HORIZONTAL ELLIPSIS pi interactions, and each tetramer aligned in one dimension along the c-axis to form two types of channels. One channel was partially penetrated by a supramolecular cation from the +/- a-axis direction, dividing the channel in the form of a bamboo node. Dy2POM was spatially divided by this bamboo node, which magnetically isolated one portion from the other. The temperature dependence of the magnetic susceptibility indicated a weak ferromagnetic interaction between the Dy ions bridged by fluoride. Dy2POM exhibited the magnetic relaxation characteristics of a single-molecule magnet, including the dependence of AC magnetic susceptibility on temperature and frequency. Magnetic relaxation can be described by the combination of thermally active Orbach and temperature-independent quantum tunneling processes. The application of a static magnetic field effectively suppressed the relaxation due to quantum tunneling.

Cooperation between single-molecule magnets and electrical conductivity holds promise for preparing high-density magnetic devices; however, there are only a few reports so far. Here we report a 4f-π-based molecular hybrid, k-(ET)5Dy(NCS)7(KCl)0.5 (1) (ET = bis(ethylenedithio)tetrathiafulvalene, NCS- = thiocyanate), which undergoes slow relaxation of the magnetization and electrical conductivity. Unlike common ET-based conductive salts, K+ ions were intercalated into ET layers and coordinated with ET radicals. We found that the ET charges were sensitive to temperature, resulting in rich conductive phases at 75-300 K. In particular, the upturn in conductivity with a clear hysteresis loop was explained by the formation of partially oxidized states with charges close to 0.5+, which accounts for a metallic state. From the results of electronic structure calculations, the hole concentration increased to 125 K, which is consistent with a partially oxidized state upon cooling. The weak antiferromagnetic interactions accompanied by a dual magnetic relaxation process below 4 K are closely associated with the weak 4f-π interactions.

Tethering metal complexes, like [Ru(bpy)

A binary system consisting of a ditopic planar pseudo-pincer ligand (qlca = quinoline-2-carbaldehyde (pyridine-2-carbonyl) hydrazone) coordinated to two metal centres affording [{Ru(bpy)2}(μ-qlca)NiCl2]Cl·4H2O·CH3OH (2) (bpy = 2,2'-bipyridine) is reported. The Ni2+ moiety acts as the electrocatalytic active site for CO2 reduction to CO. The turnover frequency (TOF) increased from 0.83 s-1 for [Ni(qlca)Cl2] (3) to 120 s-1 for 2, and the overpotential is 350 mV less than that for 3 due to the electronic influence of the {Ru(bpy)2}2+ moiety on the catalytic active site.

A heterometallic Tb-Pt complex, [Tb2 Pt3 (SAc)12 (H2 O)2 ] (SAc=thioacetate), was synthesized. Dual emission was modulated by the presence of a heterometallic Tb-Pt bonding environment. The heterometallic Tb-Pt bond lowers the symmetry of the Tb ion and enhanced the emission efficiency. In addition, the Tb-Pt complex shows field-induced multiple magnetic relaxation pathways. Furthermore, it served as an antenna for the observed dual emission. In other words, the heterometallic Tb-Pt bond has a significant effect on the luminescence and magnetic properties of the complex.

The work in this present investigation reports the syntheses, crystal structures and magnetic properties of five dinuclear lanthanide complexes having compositions [Tb2(HL)4(NO3)6] (1), [Tb2(HL)4Cl6]·2EtOH (2), [Yb2(HL)4(NO3)6] (3), [Yb2(HL)4Cl6]·2EtOH (4) and [Y2(HL)4(NO3)6] (5) with HL = 8-hydroxyquinaldine. It is evident from the crystal structures that the coordination number of trivalent lanthanide ions in compounds 1, 3 and 5 is nine, whereas that for compounds 2 and 4 is six. A dynamic magnetic study shows that both compounds 1 and 3 exhibit single-molecule-magnet (SMM) behavior while compounds 2 and 4 do not have any SMM property.

Multifunctional molecular materials exhibiting electrical conductivity and single-molecule magnet (SMM) behaviour are particularly attractive for electronic devices and related applications owing to the interaction between electronic conduction and magnetization of unimolecular units. The preparation of such materials remains a challenge that has been pursued by a bi-component approach of combination of SMM cationic (or anionic) units with conducting networks made of partially oxidized (or reduced) donor (or acceptor) molecules. The present status of the research concerning the preparation of molecular materials exhibiting SMM behaviour and electrical conductivity is reviewed, describing the few molecular compounds where both SMM properties and electrical conductivity have been observed. The evolution of this research field through the years is discussed. The first reported compounds are semiconductors in spite being able to present relatively high electrical conductivity, and the SMM behaviour is observed at low temperatures where the electrical conductivity of the materials is similar to that of an insulator. During the recent years, a breakthrough has been achieved with the coexistence of high electrical conductivity and SMM behaviour in a molecular compound at the same temperature range, but so far without evidence of a synergy between these properties. The combination of high electrical conductivity with SMM behaviour requires not only SMM units but also the regular and as far as possible uniform packing of partially oxidized molecules, which are able to provide a conducting network.

A photo-switchable single molecule-magnet (SMM) with two Dy ions bridged by a bis-bipyridine-dithienylethene ligand was synthesised. Isomerisation effects on the magnetic properties were investigated. Particular attention was paid to the slow relaxation of the magnetisation in order to determine precisely the role played by the ligand. Photo-isomerization of the ligand induced a geometric rearrangement of the complex and an electronic reconfiguration. The changes were studied by solid and solution state magnetic measurements.

Heterometallic Gd-Pt complexes ([Gd

International audience; (TTF-salphen)M compounds (TTF-salphen(2-)=4,5-bis(propylthio)tetrathiafulvalene-N,N'-phenylenebis(salicylideneimine) dianion; M=Cu(II) and Ni(II)) have been treated with Ln(hfac)(3)*2H(2)O precursors (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion; Ln=Gd(III), Tb(III), and Dy(III)) to elaborate unprecedented 3d/4f TTF-based heterobimetallic complexes of formula [(TTF-salphen)MLn(hfac)(3)]. All the structures of these compounds have been resolved by X-ray diffraction on single crystals. The structures of these complexes are formed by a TTF-salphen(2-) ligand coordinated to the 3d metal ions in the inert tetradentate N(2)O(2) site. The Ln(hfac)(3) fragment is coordinated to the (TTF-salphen)M one through the two phenolate bridges. Even if the complexes are similar in both Cu(II) and Ni(II) families, the crystal packing is different. In the first case, dimers of TTF-salphen(2-) donors constitute the organic network. In the other case, a reminiscent organic network is observed with S***S contacts. The photophysical properties of [(TTF-salphen)CuDy(hfac)(3)] (3) in chloroform solution highlight the redshift of the TTF→salphen charge transfer (400 cm(-1)) relative to the analogue excitations in (TTF-salphen)Cu, which attest to the stability of these structures in solution. Static magnetic measurements have allowed us to quantify the ferromagnetic interactions (J=+1.29 cm(-1)) between Cu(II) and Gd(III) in the [(TTF-salphen)CuGd(hfac)(3)] complex. Finally, an empirical method that consists of the comparisons of the magnetic properties of [(TTF-salphen)CuTb(hfac)(3)] with [(TTF-salphen)NiTb(hfac)(3)] and [(TTF-salphen)CuDy(hfac)(3)] with [(TTF-salphen)NiDy(hfac)(3)] has established that ferromagnetic interactions take place between Cu(II) and Tb(III) ions, whereas unusual antiferromagnetic interactions have been identified between Cu(II) and Dy(III) ions.