55Mn NMR in Mn12 acetate: Hyperfine interaction and magnetic relaxation of cluster

The 55Mn NMR in oriented powder Mn12Ac has been investigated at 1.4-2.0 K in zero field and with external fields along the c-axis. Three kinds of 55Mn NMR composed of five-fold quadrupole-split lines for I=5/2 nuclei have been interpreted to arise from Mn4+ ion, and two crystallographically-inequivalent Mn3+ ions, respectively. It is found that the isotropic hyperfine field in the Mn4+ ion with 3d3 configuration indicates a large amount of reduction (26%) as compared with the theoretical evaluation. In the analysis for the hyperfine field of Mn3+ ions with 3d4 configuration, we have taken into account of the anisotropic dipolar contribution in addition to the Fermi-contact term in order to explain two kinds of 55Mn NMR frequencies in Mn3+ ions in inequivalent sites. By using the hyperfine coupling constants of twelve manganese ions in Mn12Ac, the total hyperfine interaction of the ferrimagnetic ground state of S=10 has been determined to amount to 0.3 cm-1 in magnitude at most, the magnitude of which corresponds to the nuclear hyperfine field he(0.32 kG seen by Mn12 cluster spin. The relaxation of the cluster magnetization was investigated by observing the recovery of the 55Mn spin-echo intensity in the fields of 0.20-1.90 T along the c-axis at 2.0 K. It was found that the magnetization of the cluster exhibits the (t-recovery in the short time regime. The relaxation time decreases with increasing external field following significant dips at every 0.45 T. This is interpreted to be due to the effects of thermally-assisted quantum tunneling between the spin states at magnetic level crossings.Comment: Text 25 pages, five figures and two table

Rate-determining process in MISIM photocells for optoelectronic conversion using photo-induced pure polarization current without carrier transfer across interfaces

Recently, we proposed a [metal|insulator|semiconductor|insulator|metal] (MISIM) photocell, as a novel architecture for high-speed organic photodetectors. The electric polarization in the S layer, induced by modulated light illumination, propagates into the outside circuit as a polarization current through the I layers, without any carrier transfer across the interfaces. In the present work, we examined the MISIM photocells consisting of zinc-phthalocyanine(ZnPc)-C60 bilayers for the S layer and Parylene C for the two I layers, to understand the fundamental aspects of the MISIM photocells, such as current polarity and modulation-frequency dependence. It was found that, in such devices, the current polarity was primarily determined by the polarization in the S layer, which was induced by the donor–acceptor charge-transfer upon illumination. Furthermore, the ON and OFF current, which appeared in the periods of illumination-on and -off, respectively, exhibited significantly different dependence on the modulation frequency. This was well-explained by an imbalance between a quick polarization in the S layer during illumination and its slow relaxation in the dark

Fluorination induced electronic effects on Pt(II) square-planar complex of o-phenylenediimine ligand

A novel complex [Pt(C6F4(NH)2)2] (2), formed by a Pt(ii) cation bound to two molecules of the tetrafluorinated 1,2-phenylenediimine ligand, has been synthesized and characterized by electrochemical and XRD measurements, UV-vis-NIR spectroscopy as well as by DFT and TD-DFT calculations. The effect induced by the fluorine atoms has been highlighted by comparison with the corresponding Ni (1H) and Pt (2H) hydrogenated complexes. The cyclic voltammetry data show that the reduction and the oxidation processes of 2 are easier and more difficult (by about 0.5 V), respectively, compared to those of 1H and 2H, suggesting that the electron withdrawing ability of the fluorine atoms lowers the energy level of both the HOMO and the LUMO. UV-vis-NIR measurements are similar for all the three complexes, indicating similar HOMO-LUMO gaps and that the effects of fluorination on the frontier orbitals are roughly the same. Moreover, polymorphism in the powder form of 2 has been highlighted by XRD measurements while the film presents only one phase. Furthermore, this complex shows a field-effect for n-type carriers. All the experimental results are also supported by the calculations, which show the role played by the fluorine atoms in the electronic structure of 2

Controlling the crystallinity and crystalline orientation of “shuttlecock” naphthalocyanine films for near-infrared optoelectronic applications

The thin film properties of tin(II) 2,3-naphthalocyanine (SnNPc) were interrogated and various strategies for controlling the crystallinity and crystalline orientation within the films were assessed. SnNPc is shown to crystallize in the space group P21/c (Z = 4), where the molecular arrangement consists of alternating layers of concave and convex overlap, induced by the out-of-plane Sn atoms, resulting in a 3D slipped-π-stack network structure analogous to that reported for Phase I of titanyl phthalocyanine. The thin films were studied by X-ray diffraction, atomic force microscopy and absorption spectroscopy and are highly sensitive not just to the conditions during growth, but also to substrate pre- and post-deposition treatment. While the films grown at room temperature were largely amorphous, the crystallinity was enhanced with substrate temperature, with the molecules orienting in a standing molecular geometry. A thin layer of 3,4:9,10-perlenetetracarboxylic dianhydride induces a lying molecular geometry of the same polymorph as that of the single crystal, while different polymorphs are accessible through solvent vapor annealing of amorphous films. Transient photocurrent measurements showed a dramatic improvement in photodetector device bandwidth for the lying molecular geometry, which was attributed to enhanced photoconductivity along the π-stacking axis, while solvent vapor annealing could be used to tune the photosensitivity across the near-infrared region

Pressure-Induced Ferromagnetic to Nonmagnetic Transition and the Enhancement of Ferromagnetic Interaction in the Thiazyl-Based Organic Ferromagnet γ-BBDTA·GaCl4

A thiazyl-based ferromagnet, the γ-phase of BBDTA (i.e., benzo[1,2- d :4,5- d \u27]bis[1,3,2]dithiazole)·GaCl 4 , has a high ferromagnetic ordering temperature of 7.0 K in organic radical ferromagnets. In this system, pressurization generated more compact molecular packing, resulting in that the ferromagnetic state at P = 16.2 kbar is stabilized over a temperature range of more than twice of the initial range. However, the saturation magnetic moment was reduced with increasing pressure, decreasing to about 12% of the initial value even at the low pressure level of P = 1.0 kbar. This suggests that the ferromagnetic molecular packing of the monoclinic γ-phase is easily transformed into that of the diamagnetic phase. Powder X-ray diffraction experiments revealed that the diamagnetic non-monoclinic (α- or β-) phase became stable instead of the monoclinic γ-phase across the pressure of 2.5–5.8 kbar. The increase in the temperature of onset of ferromagnetic state occurs in the surviving ferromagnetic domain surrounded by the diamagnetic domains