Ordered patterning of nanometric rings of single molecule magnets on polymers by lithographic control of demixing

We report a new patterning process which takes place as a result of demixing of a binary polymer/solute mixture. An efficient, sustainable approach for ordering nanosized rings of so-called single molecule magnets (SMMs) is thus provided. It exploits the self-organization process in which SMM patterned film evolves to a spatially correlated pattern of nanosized rings. At long time, the anisotropic patterning of the film drives the ring to coalesce, into parallel lines of nanometric width.     

A three-dimensional lanthanide-organic radical open-framework

The reaction of a 3-connecting PTMTC radical with Tb(III) ions forms a three-dimensional open-framework with the formula [Tb(PTMTC)(DMF)(3)] (1), which associates a lattice complex T topology with large channels, guest-induced reversible crystal to amorphous transformations and ferromagnetic metal-radical interactions.     

Transition metal bisdithiolene complexes based on extended ligands with fused tetrathiafulvalene and thiophene moieties: new single-component molecular metals

The gold and nickel bisdithiolene complexes based on new highly extended ligands incorporating fused tetrathiafulvalene and thiophene moieties (alpha-tdt=thiophenetetrathiafulvalenedithiolate and dtdt=dihydro- thiophenetetrathiafulvalenedithiolate), were prepared and characterised by using cyclic voltammetry, single crystal X-ray diffraction, EPR, magnetic susceptibility and electrical transport measurements. These complexes, initially obtained under anaerobic conditions as diamagnetic gold monoanic [nBu(4)N][Au(alpha-tdt)(2)] (4), [nBu(4)N][Au(dtdt)(2)] (3) and nickel dianionic species [(nBu(4)N)(2)][Ni(alpha-tdt)(2)] (8), [(nBu(4)N)(2)][Ni(dtdt)(2)] (7), can be easily oxidised to the stable neutral state just by air or iodine exposure. The monoanionic complexes crystallise in at least two polymorphs, all of which have good cation and anion segregation in alternated layers, the anion layers making a dense 2D network of short SS contacts. All of the neutral complexes, obtained as microcrystalline or quasi amorphous fine powder, present relatively large magnetic susceptibilities that correspond to effective magnetic moments in the range 1-3 mu(B) indicative of high spin states and very high electrical conductivity that in case of the Ni compound can reach sigma(RT) approximately 250 S cm(-1) with a clear metallic behaviour. These compounds are new examples of the still rare single-component molecular metals.     

Electroactive thiazole derivatives capped with ferrocenyl units showing charge-transfer transition and selective ion-sensing properties: a combined experimental and theoretical study

The synthesis, optical and electrochemical properties, and X-ray characterization of two thiazole derivatives capped by ferrocenyl groups (5 and 7) and their model compounds with one ferrocenyl, either at 2 or 5 position of the mono- or bis-thiazolyl rings (3, 9, 11, and 14), are presented. Bisferrocenyl thiazole 5 forms the mixed-valence species 5*+ by partial oxidation which, interestingly, shows an intramolecular electron-transfer phenomenon. Moreover, the reported heteroaromatic compounds show selective ion-sensing properties. Thus, ferrocenylthiazoles linked across the 5 position of the heteroaromatic ring are selective chemosensors for Hg2+ and Pb2+ metal ions; 5-ferrocenylthiazole 3 operates through two channels, optical and redox, for Hg2+ and only optical for Pb2+, whereas 1,1'-bis(thiazolyl)ferrocene 14 is only an optical sensor for both metal ions. Moreover, complex 3 behaves as an electrochemically induced switchable chemosensor because of the low metal-ion affinity of the oxidized 3*+ species. On the other hand, ferrocenylthiazole 9, in which the heterocyclic ring and the ferrocene group are linked across the 2 position, is a selective redox sensor for Hg2+ metal ions, and it responds optically, as does bis(thiazolyl)ferrocene 11, to a narrow range of cations (Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+). Finally, bis(ferrocenyl)thiazole 5 is a dual optical and redox sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+, whereas bis(ferrocenyl) compound 7, bearing a bis(thiazole) unit as a bridge, is only a chromogenic sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+. The experimental data and conclusions about both the electronic and ion-sensing properties are supported by DFT calculations which show, in addition, an unprecedented intramolecular electron-transfer reorganization after the first one-electron oxidation of compound 5.     

Towards the detection of single polychlorotriphenylmethyl radical derivatives by means of Electron Spin Noise STM

The Electron Spin Noise Scanning Tunnelling Microscopy (ESN-STM) technique is one of the most promising techniques detecting one single spin, combining the spatial resolution of the STM with the ability of spectral resolution and spin manipulation of Electron Spin Resonance. After its first observation, the effectiveness of this technique has been tested by different groups to study the properties of small aggregates or single organic radical molecules.We report on the ongoing ESN-STM study on nano-aggregates of tris(2,4,6-thrichlorophenyl)methyl radical (TTM) derivatives, whose possibility to be used as wires, switches and memory devices has already been investigated in bulk. After deposition on Au(111), TTM radicals preserved their magnetism. To treat the collected noise data we followed a statistical approach; some peculiar characteristics of this analysis will be addressed.     

Experimental and theoretical studies of magnetic exchange in silole-bridged diradicals

Five bis(tert-butylnitroxide) diradicals connected by a silole (7 a-d) or a thiophene (12) ring as a coupler were studied. Compound 12 crystallizes in the orthorhombic space group Pna2(1) with a = 20.752(5), b = 5.826(5), and c = 34.309(5) A. X-ray crystal structure determination, electronic spectroscopy, variable-temperature EPR spectroscopy, SQUID measurements and DFT computations (UB3LYP/6-31+G*) were used to study the molecular conformations and electronic spin coupling in this series of molecules. Whereas compounds 7 b, 7 c, and 7 d are quite stable both in solution and in the solid state, 7 a and 12 undergo a partial electronic rearrangement to both a diamagnetic quinonoidal form and a monoradical species owing to the fact that they correspond to the open form of a pi-conjugated Kekulé structure. In the solid state, magnetic measurements indicate that the diradicals are all antiferromagnetically coupled, as expected from their topology. These interactions are best reproduced by means of a "Bleaney-Bowers" model that gives values of J = -142.0 cm(-1) for 7 a, -1.8 cm(-1) for 7 b, -1.3 cm(-1) for 7 c, -4.2 cm(-1) for 7 d, and -248.0 cm(-1) for 12. The temperature dependence of the EPR half-field transition in frozen dichloromethane solutions is consistent with singlet ground states and thermally accessible triplet states for diradicals 7 b, 7 c, and 7 d with DeltaE(T-S) values of 3.48, 2.09, and 8 cm(-1), respectively. No evidence of a populated triplet state was found for diradicals 7 a and 12. Similarities between the DeltaE(T-S) and J values (DeltaE(T-S) = -2 J) clearly show the intramolecular origin of the observed antiferromagnetic interaction. Analyses of the data with a "Karplus-Conroy"-type equation enabled us to establish that the silole ring, as a whole, allows a more efficient magnetic coupling of the two nitroxide radicals attached to its 2,5-positions than the thiophene ring. This superiority probably originates from the nonaromaticity of the silole which thus permits a better magnetic interaction through it. DFT calculations also support the experimental results, indicating that the magnetic exchange pathway preferentially involves the carbon pi system of the silole.     

A Phenyl α-Nitronyl Nitroxide with a Forced Chiral Conformation

Summary.  A new phenyl α-nitronyl nitroxide bearing a hydroxyl group at position 2 of the aromatic ring and a chiral methyl lactate substituent at position 5 has been synthesized with the aim of combining the magnetic properties of this kind of radical with the optical properties endowed by the chiral group. The optically active compound forms intramolecular hydrogen bonds between the OH group and one of the NO groups and shows a large torsion angle between the two rings when compared with similar radicals with no substituent in this position. Therefore, the optical properties are distinct. The optical and magnetic properties of the new radical in both solution and solid state are presented. Received June 23, 2000. Accepted (revised) September 18, 2000