Tetranuclear Dysprosium(III) Quintuple-Decker Single-Molecule Magnet Prepared Using a π-Extended Phthalocyaninato Ligand with Two Coordination Sites.

The magnetic properties and spin relaxation processes of a tetranuclear dysprosium(III) fused phthalocyaninato (Pc ) quintuple-decker single-molecule magnet (SMM) (1) with non-equivalent octa-coordination geometries are reported. The structure of 1 is regarded as a dimer of Dy -Pc triple-decker SMMs with different magnetic relaxation characteristics, corresponding to the octa-coordination geometry sites Dy1 with C symmetry (ϕ =23°) and Dy2 with D symmetry (ϕ =45°). In an H of 1750 Oe and T range of 1.

Comparison of the Magnetic Anisotropy and Spin Relaxation Phenomenon of Dinuclear Terbium(III) Phthalocyaninato Single-Molecule Magnets Using the Geometric Spin Arrangement.

Herein we report the synthesis and characterization of a dinuclear Tb single-molecule magnet (SMM) with two [TbPc] units connected via a fused-phthalocyaninato ligand. The stable and robust complex [(obPc)Tb(Fused-Pc)Tb(obPc)] (1) was characterized by using synchrotron radiation measurements and other spectroscopic techniques (ESI-MS, FT-IR, UV). The magnetic couplings between the Tb ions and the two π radicals present in 1 were explored by means of density functional theory (DFT).

Elucidation of Dual Magnetic Relaxation Processes in Dinuclear Dysprosium(III) Phthalocyaninato Triple-Decker Single-Molecule Magnets Depending on the Octacoordination Geometry.

When applying single-molecule magnets (SMMs) to spintronic devices, control of the quantum tunneling of the magnetization (QTM) as well as a spin-lattice interactions are important. Attempts have been made to use not only coordination geometry but also magnetic interactions between SMMs as an exchange bias. In this manuscript, dinuclear dysprosium(III) (Dy ) SMMs with the same octacoordination geometry undergo dual magnetic relaxation processes at low temperature.

How Ions Arrange in Solution: Detailed Insight from NMR Spectroscopy of Paramagnetic Ion Pairs.

Ion pairing between the paramagnetic anion [Tb(obPc) ] (obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), which has a very large magnetic anisotropy, with various diamagnetic counterions [P(Ph) ] (1 a), [As(Ph) ] (1 b), bis(triphenylphosphine)iminium ([PPN] , 1 c) and tetra-n-butylammonium ([TBA] , 1 d) was studied by means of H, C, N, and P NMR spectroscopy in solution at various temperatures. The influence of the paramagnetic anion on the NMR spectroscopy properties of the diamagnetic cations allowed a detailed insight into the distances and relative orientations of the paired ions. Isotropic tumbling models for the description of the quaternary cations are inaccurate, particularly for [TBA] with its flexible butyl chains.

α-Substituted Bis(octabutoxyphthalocyaninato)Terbium(III) Double-Decker Complexes: Preparation and Study of Protonation by NMR and DFT.

Synthesis of the anionic, α-substituted, bis(phthalocyaninato)Tb(III) complex [Tb(α-obPc)2](-) ([1](-)) (obPc = α-octabutoxyphthalocyaninato) leads to the isolation of its protonated form [1H](0). This complex was characterized by X-ray diffraction (XRD), mass spectroscopy (MS), infrared (IR) and ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy. Crystal structure analysis did not allow localization of the additional proton, which is probably attached to the meso-N atom or isoindole-N atom of the phthalocyaninato ligand.

Ligand π-radical interaction with f-shell unpaired electrons in phthalocyaninato-lanthanoid single-molecule magnets: a solution NMR spectroscopic and DFT study.

The phthalocyaninato double-decker complexes [M(obPc)2 ](0) (M= Y(III) , Tb(III) , Dy(III) ; obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), along with their reduced ([M(obPc)2 ](-) [P(Ph)4 ](+) ; M=Tb(III) , Dy(III) ) and oxidized ([M(obPc)2 ](+) [SbCl6 ](-) (M=Y(III) , Tb(III) ) counterparts were studied with (1) H, (13) C and 2D NMR. From the NMR data of the neutral (i.e.

Fully electron-transferred donor/acceptor layered frameworks with TCNQ(2-).

In a series of two-dimensional layered frameworks constructed by two electron-donor (D) and one electron-acceptor (A) units (a D2A framework), two-electron transferred systems with D(+)2A(2-) were first synthesized as [{Ru2(R-PhCO2)4}2(TCNQRx)]·n(solv) (R = o-CF3, Rx = H2 (1), R = o-CF3, Rx = Me2 (2), R = o-CF3, Rx = F4 (3), R = o-Me, TCNQRx = BTDA-TCNQ (4), R = p-Me, TCNQRx = BTDA-TCNQ (5), where TCNQ is 7,7,8,8-tetracyano-p-quinodimethane and BTDA-TCNQ is bis[1,2,5]dithiazolotetracyanoquinodimethane). The D(+)2A(2-) system was synthesized by assembling D/A combinations of paddlewheel-type [Ru2(II,II)(R-PhCO2)4] complexes and TCNQRx that possibly caused a large gap between the HOMO of D and the LUMO of A (ΔEH-L(DA)). All compounds were paramagnetic because of quasi-isolated [Ru2(II,III)](+) units with weakly antiferromagnetically coupled S = 3/2 spins via diamagnetic TCNQRx(2-) and/or through the interlayer space.

Effect of f-f interactions on quantum tunnelling of the magnetization: mono- and dinuclear Dy(III) phthalocyaninato triple-decker single-molecule magnets with the same octacoordination environment.

The single-molecule magnet (SMM) behaviour of dinuclear Ln(III)-Pc triple-decker complexes (Dy(III)-Y(III): 1 and Dy(III)-Dy(III): 2) with the same octacoordination environment and slow magnetic relaxation behaviour were explained using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of dinuclear Dy(III)-Pc triple-decker type SMMs have never been discussed on the basis of the same octacoordination environment. Our results clearly show that the Dy(III) ion sites of 1 and 2 are equivalent, consistent with the crystal structure.

Controlling the dipole-dipole interactions between terbium(III) phthalocyaninato triple-decker moieties through spatial control using a fused phthalocyaninato ligand.

Using a fused phthalocyaninato ligand to control the spatial arrangement of Tb(III) moieties in Tb(III) single-molecule magnets (SMMs), we could control the dipole-dipole interactions in the molecules and prepared the first tetranuclear Tb(III) SMM complex. [Tb(obPc)2]Tb(Fused-Pc)Tb[Tb(obPc)2] (abbreviated as [Tb4]; obPc = 2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato, Fused-Pc = bis{7(2),8(2),12(2),13(2),17(2),18(2)-hexabutoxytribenzo[g,l,q]-5,10,15,20-tetraazaporphirino}[b,e]benzenato). In direct-current magnetic susceptibility measurements, ferromagnetic interactions among the four Tb(3+) ions were observed.

First observation of a Kondo resonance for a stable neutral pure organic radical, 1,3,5-triphenyl-6-oxoverdazyl, adsorbed on the Au(111) surface.

We investigated spin states of stable neutral pure-organic radical molecules of 1,3,5-triphenyl-6-oxoverdazyl (TOV) and 1,3,5-triphenyl-6-thioxoverdazly (TTV) adsorbed on an Au(111) surface, which appears as a Kondo resonance because of spin-electron interaction. By using scanning tunneling spectroscopy (STS), a clear Kondo resonance was detected for the TOV molecule. However, no Kondo resonance was detected for TOV molecules with protrusions in the occupied state image and for TTV molecules.

A three-dimensional network of two-electron-transferred [Ru2]2TCNQ exhibiting anomalous conductance due to charge fluctuations.

A new D(2)A-type charge-transfer three-dimensional network with a charge distribution of [{Ru(2)}(δ+)-(BTDA-TCNQ(2δ-))-{Ru(2)}(δ+)] where δ ≈ 1, which exhibits a sudden decrease in electronic resistance, formed from the assembly of a paddlewheel diruthenium(II, II) complex ([Ru(2)]) as a donor (D) and bis(1,2,5-thiadiazolo)tetracyanoquinodimethane (BTDA-TCNQ) as an acceptor (A).