Solid-state ligand-driven light-induced spin change at ambient temperatures in bis(dipyrazolylstyrylpyridine)iron(II) complexes

We previously reported that an Fe(II) complex ligated by two (Z)-2,6-di(1H-pyrazol-1-yl)-4-styrylpyridine ligands (Z-H) presented a solid state ligand-driven light-induced spin change (LD-LISC) upon one-way Z-to-E photoisomerization, although modulation of the magnetism was trivial at ambient temperatures (Chem. Commun.2011, 47, 6846). Here, we report the synthesis of new derivatives of Z-H, Z-CN and Z-NO(2), in which electron-withdrawing cyano and nitro substituents are introduced at the 4-position of the styryl group to attain a more profound photomagnetism at ambient temperatures. Z-CN and Z-NO(2) undergo quantitative one-way Z-to-E photochromism upon excitation of the charge transfer band both in acetonitrile and in the solid state, similar to the behavior observed for Z-H. In solution, these substituents stabilized the low-spin (LS) states of Z-CN and Z-NO(2), and the behavior was quantitatively analyzed according to the Evans equation. The photomagnetic properties in the solid state, on the other hand, cannot be explained in terms of the substituent effect alone. Z-CN displayed photomagnetic properties almost identical to those of Z-H. Z-CN preferred the high-spin (HS) state at all temperatures tested, whereas photoirradiated Z-CN yielded a lower χ(M)T at ambient temperatures. The behavior of Z-NO(2) was counterintuitive, and the material displayed surprising photomagnetic properties in the solid state. Z-NO(2) occupied the LS state at low temperatures and underwent thermal spin crossover (SCO) with a T(1/2) of about 270 K. The photoirradiated Z-NO(2) displayed a higher value of χ(M)T and the modulation of χ(M)T exceeded that of Z-H or Z-CN. Z-NO(2)·acetone, in which acetone molecules were incorporated into the crystal lattice, further stabilized the LS state (T(1/2) > 300 K), thereby promoting large modulations of the χ(M)T values (87% at 273 K and 64% at 300 K) upon Z-to-E photoisomerization. Single crystal X-ray structure analysis revealed that structural factors played a vital role in the photomagnetic properties in the solid state. Z-H and Z-CN favored intermolecular π-π stacking among the ligand molecules. The coordination sphere around the Fe(II) nucleus was distorted, which stabilized the HS state. In contrast, Z-NO(2)·acetone was liberated from such intermolecular π-π stacking and coordination distortion, resulting in the stabilization of the LS state.     

High-lift airfoil trailing edge separation control using a single dielectric barrier discharge plasma actuator

Control of flow separation from the deflected flap of a high-lift airfoil up to Reynolds numbers of 240,000 (15 m/s) is explored using a single dielectric barrier discharge (DBD) plasma actuator near the flap shoulder. Results show that the plasma discharge can increase or reduce the size of the time-averaged separated region over the flap depending on the frequency of actuation. High-frequency actuation, referred to here as quasi-steady forcing, slightly delays separation while lengthening and flattening the separated region without drastically increasing the measured lift. The actuator is found to be most effective for increasing lift when operated in an unsteady fashion at the natural oscillation frequency of the trailing edge flow field. Results indicate that the primary control mechanism in this configuration is an enhancement of the natural vortex shedding that promotes further momentum transfer between the freestream and separated region. Based on these results, different modulation waveforms for creating unsteady DBD plasma-induced flows are investigated in an effort to improve control authority. Subsequent measurements show that modulation using duty cycles of 50–70% generates stronger velocity perturbations than sinusoidal modulation in quiescent conditions at the expense of an increased power requirement. Investigation of these modulation waveforms for trailing edge separation control similarly shows that additional increases in lift can be obtained. The dependence of these results on the actuator carrier and modulation frequencies is discussed in detail.     

Wavelength-conversion type picosecond optical switching using a waveguide QPM-SHG/DFG device

We report picosecond all-optical switching in optical communication band using a LiNbO₃ waveguide quasi-phase matched second-harmonic generation/difference-frequency generation device. Analysis based on the beam propagation method showed that 1 ps switching with 3.1% efficiency is feasible with 10 W peak control pulse power. Switching efficiency of ?22 dB was demonstrated using control pulses of 10 ps width and 2 W peak power.     

The agency problem between the owner and the manager in real investment: The bonus-audit relationship

This paper derives the owner’s optimal contract with a bonus-incentive and audit when the owner delegates the investment timing decision to a manager with private information on an investment project. The optimal solution not only unifies the previous studies, but also accounts for actual auditing systems in firms.     

Porous microfibers and microhoneycombs synthesized by ice templating

Recently we introduced the “ice templating” method, a new method which allows the synthesis of nanoporous materials with unique morphology, such as microfibers and microhoneycombs. In this method, materials are synthesized by freezing their parent hydrosols or hydrogels unidirectionally. Ice crystals which grow within the precursor during freezing act as the template. Therefore, the template can be easily removed through simple thawing and drying, which is a unique and beneficial feature of this method. This paper will first describe the outline of this new method and next, the details about methods to control the dimensions of the materials obtained through it. Comments about the range of applicability of this method will also be provided.     

Photochemical behavior of azobenzene-conjugated CoII, CoIII, and FeII bis(terpyridine) complexes

Azobenzene-conjugated mononuclear and dinuclear terpyridyl complexes of Co(II), Co(III), and Fe(II) were synthesized, and their photoisomerization behavior was investigated. Co(II) and Co(III) complexes, [tpyCo(tpy-AB)]X(n) and [(Cotpy)(2)(tpy-AB-tpy)]X(n) (tpy-AB = C(15)N(3)H(10)-C(6)H(4)-N=NC(6)H(5), tpy-AB-tpy = C(15)N(3)H(10)-C(6)H(4)-N=NC(6)H(4)-C(15)N(3)H(10), X = PF(6) or BPh(4)), exhibit trans-to-cis photoisomerization by irradiation at 366 nm, and this behavior is dependent on solvents and counterions. For the Co(II) complexes, BPh(4) salts undergo cis-to-trans isomerization in propylene carbonate by both photoirradiation with visible light (435 nm) and heat, indicating that reversible trans-cis isomerization has occurred. [Co(tpy-AB)(2)](BPh(4))(2) shows a two-step trans-to-cis isomerization process. The trans-cis isomerization behavior of Co(III) complexes was observed only in the solvents with a low donor number such as 1,2-dichloroethane. Fe(II) complexes, [tpyFe(tpy-AB)]X(n) (X = PF(6) or BPh(4)), exhibit slight trans-to-cis photoisomerization due to the energy transfer from the azobenzene moiety to Fe(tpy)(2) moieties.