Search

Two mononuclear complexes [Ni(dapsc)(H2O)2]Cl(NO3)·H2O (1) and [Ni(dapsc)(NCS)2] (2), and a bimetallic CN-bridged trinuclear molecule [NiII(dapsc)(H2O)]2[WIV(CN)8]·11H2O (3) (dapsc = 2,6-diacetylpyridine-bis(semicarbazone)) were synthesised and characterised in terms of structure and magnetic properties. All three compounds contain Ni(II) ions in a pentagonal bipyramid coordination geometry afforded by the equatorial pentadentate ligand (dapsc) and two O- or N-donating axial ligands. The compounds differ in the relative arrangement of the complexes, intermolecular interactions and distortion from the ideal coordination geometry. The high-field EPR and magnetometric studies show large anisotropy of the Ni(II) centres with the D parameters in the range of −10.5 to −21.2 cm−1 and negligible antiferromagnetic interactions. The easy-axis magnetic anisotropies of 1–3 were reproduced by ab initio CASSCF/NEVPT2 calculations. The ground states consist mainly of the |MS〉 = |±1〉 states, which is consistent with the fact that no out-of-phase signal can be detected in the AC magnetic susceptibility measurements.

We introduce some representative studies from our laboratory, mostly from the 21st Century. We are interested in the synthesis, optical spectroscopy, such as magnetic circular dichroism (MCD), circ...

Novel hexabutylsulphonyltribenzotetraazachlorin–fullerene (C60) complexes of iron (FeHBSTBTAC–C60) and cobalt (CoHBSTBTAC–C60) have been synthesized and their electrochemistry and oxygen reduction reaction (ORR) compared with their octabutylsulphonylphthalocyanine analogues (FeOBSPc and CoOBSPc). It is proved that electron-withdrawing substituents (–SO2Bu and C60) on phthalocyanine macrocycle exhibit distinct impact on the solution electrochemistry of these metallophthalocyanine (MPc) complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu in alkaline medium. FeOBSPc showed the best ORR activity involving a direct 4-electron mechanism, a rate constant of ∼1 × 108 cm3 mol−1 s−1 and a Tafel slope of −171 mV dec−1. Keywords: Metal (Fe, Co) phthalocyanine–C60, Cyclic voltammetry, RDE experiment, Oxygen reduction

Nuclear spin driven quantum tunneling of magnetization (QTM) phenomena, which arise from admixture of more than two orthogonal electronic spin wave functions through the couplings with those of the nuclear spins, are one of the important magnetic relaxation processes in lanthanide single molecule magnets (SMMs) in the low temperature range. Although recent experimental studies have indicated that the presence of the intramolecular f-f interactions affects their magnetic relaxation processes, little attention has been given to their mechanisms and, to the best of our knowledge, no rational theoretical models have been proposed for the interpretations of how the nuclear spin driven QTMs are influenced by the f-f interactions. Since quadruple-decker phthalocyanine complexes with two terbium or dysprosium ions as the magnetic centers show moderate f-f interactions, these are appropriate to investigate the influence of the f-f interactions on the dynamic magnetic relaxation processes. In the present paper, a theoretical model including ligand field (LF) potentials, hyperfine, nuclear quadrupole, magnetic dipolar, and the Zeeman interactions has been constructed to understand the roles of the nuclear spins for the QTM processes, and the resultant Zeeman plots are obtained. The ac susceptibility measurements of the magnetically diluted quadruple-decker monoterbium and diterbium phthalocyanine complexes, [Tb-Y] and [Tb-Tb], have indicated that the presence of the f-f interactions suppresses the QTMs in the absence of the external magnetic field (H(dc)) being consistent with previous reports. On the contrary, the faster magnetic relaxation processes are observed for [Tb-Tb] than [Tb-Y] at H(dc) = 1000 Oe, clearly demonstrating that the QTMs are rather enhanced in the presence of the external magnetic field. Based on the calculated Zeeman diagrams, these observations can be attributed to the enhanced nuclear spin driven QTMs for [Tb-Tb]. At the H(dc) higher than 2000 Oe, the magnetic relaxations become faster with increasing Hdc for both complexes, which are possibly ascribed to the enhanced direct processes. The results on the dysprosium complexes are also discussed as the example of a Kramers system.

The crystal structure of 5,10,15,20-tetramethyl-21H,23H-porphine vanadium(IV) oxide, VO(TMP), has been determined. Monoclinic, P21/a, a = 14.298(5), b = 13.445(4), c = 19.895(6)A, β = 97.487(2). Z = 8, C24H20N4OV.

A novel platinum-based macrocycle, iron(II) tetrakis(diaquaplatinum)octacarboxyphthalocyanine (PtFeOCPc), was synthesised and characterised. The heterogeneous electron transfer and electrocatalytic properties of this functional material towards the oxidation of formic acid have been explored on a graphite electrode platform pre-modified with or without acid-functionalised multi-walled carbon nanotubes (MWCNTs). We prove that PtFeOCPc supported on a MWCNT platform (MWCNT–PtFeOCPc) exhibits enhanced electrochemical response in terms of (i) electron transfer towards outer-sphere redox probe, (ii) catalytic rate constant, and (iii) tolerance towards CO poisoning during formic acid oxidation. The results clearly suggest that the MWCNT–PtFeOCPc is a promising platform for potential application as an electrocatalyst for direct formic acid fuel cell.

not Available.

not Available.