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380 records · Page 22

Magnetic and EPR Spectroscopic Studies of Thiolate Bridged Divalent Ni, Pd, and Pt Ions Capped with VO(N 2 S 2 ) Metalloligands

Reactions of the metallodithiolate complex VO(bme-dach) (hereafter abbreviated as V, where bme-dach = N,N ′-bis(2-mercaptoethyl)-1,4-diazacycloheptane) with [Pd II (CH 3 CN) 4 ](BF 4 ) 2 and [Pt II (CH 3 CN) 4 ](BF 4 ) 2 yield the V–M–V trimetallic compounds [VPdV](BF 4 ) 2 (2) and [VPtV](BF 4 ) 2 (3). Reaction of a similar metalloligand, VO(bme-daco) (hereafter abbreviated as V′ where bme-daco = N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane) with [Ni II (CH 3 CN) 6 ](BF 4 ) 2 afforded the related salt [V′NiV′](BF 4 ) 2 (1). X-ray structural analyses revealed that cations in 1, 2, and 3 adopt a stairstep C 2h structure consisting of two terminal VO(N 2 S 2 ) moieties bridged via thiolate sulfur to the group 10 metal ions. Weak ferromagnetic superexchange coupling (J = 0.282 cm –1 for 1, 0.954 cm –1 for 2, and 1.372 cm –1 for 3) was observed between the two S = 1/2 V IV centers separated by distances in the range of 5.9–6.3 Å, with J values varying following the order Ni < Pd < Pt. Frozen-solution EPR spectra measured on the more soluble [BArF 24 ] − (BArF 24 – = tetrakis((3,5-trifluoromethyl)phenyl)borate) analogues revealed that the [VPtV] 2+ cation exhibits a 15-line hyperfine splitting of 225 MHz at g = 4 in parallel mode, confirming exchange coupling between the two 51 V, I = 7/2 nuclei. Density-functional theory (DFT) calculations indicate an S = 1 ground state for 1–3. These results demonstrate that the choice of paramagnetic metallodithiolate ligand and diamagnetic bridge in such trimetallic species influences the sign and magnitude of magnetic interactions.

anions↗

Error field correction strategies in preparation to MAST-U operation

In magnetic fusion devices, unwanted non-axisymmetric magnetic field perturbations, known as error fields (EF), can have detrimental effects on plasma stability and confinement. Such EFs may originate from several sources, such as axi-symmetric coil misalignments, coil feeds, 3D structures in the wall surrounding the plasma, presence of ferromagnetic materials near the plasma surface, blanket materials in future devices. To minimize their impact on plasma performance and on the available operational space, it is important to identify the EF sources and develop EF control strategies. MAST Upgrade (MAST-U) is a spherical tokamak which will operate in the near future after a series of enhancements from the previous MAST experiment. To deliver a machine with EF amplitude low enough to allow a high quality experimental programme, systematic analysis of the intrinsic EF sources has been carried out for poloidal eld (P) and divertor (D) coils. To deliver a machine with EF amplitude low enough to allow a high quality experimental programme, systematic analysis of the intrinsic EF sources has been carried out for poloidal field (P) and divertor (D) coils, whose magnetic eld measurements were available when writing this paper. Such measurements reveal that P and D coils are 3D deformed and thus are responsible for intrinsic EFs, with mainly n=1 and n=2 toroidal mode numbers. In preparation to MAST-U operation, both passive and active EF control strategies have been adopted for n=1 and n=2 EFs compensation. Passive EF control consisted of installing finely each D and P coil within MAST-U device so as to minimize the intrinsic n=1 EF amplitude. The optimal coil alignment has been determined based on magnetic eld measurements and the corresponding 3D electro-magnetic modelling, and envisaged coil shift and tilt of 3.2 mm and 0.7 mrad, respectively, in the case of P coil named P4. Conversely, active control will be use during MAST-U operation to reduce the n=2 EF which is associated mainly with P4 and P5, as well. Since these coils have been re-used from the MAST device, studies attempting n=2 EF control, based on MAST plasmas, have been modelled utilizing the MARS-F code to interpret experimental results in MAST and to give hints for future n=2 EF control studies in MAST-U. Here, a model-based control set for n=2 EF control has been identified which would allow for the minimization of rotation braking, of the resonant magnetic field at the q=2 and of the plasma displacement in MAST-U, simultaneously.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗