Precise control and consecutive modulation of spin transition temperature using chemical migration in porous coordination polymers

Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)(4)(I)(n)]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T(c) in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T(c) ad arbitrium through unique postsynthetic method using iodine migration.     

Synthesis and X-ray crystal structure of a difunctionalized pillar[5]arene at A1/B2 positions by in situ cyclization and deprotection

The reaction of 1,4-dimethoxybenzene and paraformaldehyde using AlBr(3) yields multiple-deprotected pillar[5]arenes. A1/B2 di-deprotected pillar[5]arene can be isolated by silica gel chromatography and washing procedures. The X-ray structure and polymerization of the A1/B2 di-deprotected pillar[5]arene are reported.     

The annealing behavior of hydrogen implanted into Al-1.5 at.% Si alloy

We have studied effects of added elements as well as defects on trap-sites of hydrogen in metals. For the purpose, we observed depth profiles and thermal behaviors of hydrogen implanted into Al-1.5 at.% Si alloy samples in an implantation-temperature range of liquid nitrogen temperature (LNT) to 373 K at different doses. The results were compared with those for pure aluminum samples. It was found that hydrogen is trapped as molecules in grain boundaries of Al/Si.     

Soft-landing isolation of vanadium-benzene sandwich clusters on a room-temperature substrate using n-alkanethiolate self-assembled monolayer matrixes

Gas-phase synthesized vanadium-benzene 1:2 (VBz(2)) sandwich clusters were size-selectively deposited onto bare gold and long-chain n-alkanethiolate [-S-(CH(2))(n-1)-CH(3); n = 16, 18, and 22] self-assembled monolayer (SAM)-coated gold substrates under ultrahigh vacuum (UHV) conditions. Investigation of the resulting deposited clusters was performed by infrared reflection absorption spectroscopy (IRAS) and thermal desorption spectroscopy (TDS). The IR frequencies of the soft-landed VBz(2) clusters show excellent agreement with the fundamentals reported in IR data of VBz(2) in an argon matrix. The analysis of IRAS spectra reveals that while there was no orientational preference of the VBz(2) clusters on a bare gold substrate, the VBz(2) clusters deposited onto the SAM substrates were highly oriented with the molecular axis 70-80 degrees tilted off the surface normal. In addition, analysis of TDS spectra revealed unusually large adsorption heats of the physisorbed VBz(2) clusters. The present results are explained by cluster penetration into the long-chain alkanethiolate SAM and for the first time demonstrate the matrix isolation of gas-phase organometallic clusters around room temperature.     

Effects of localized triplet exciton on reactivity of photoinduced omega-bond dissociation in naphthyl phenyl ketones having pi,pi* lowest triplet (T1) states studied by laser flash photolysis

Photochemical properties of photoinduced omega-bond dissociation in naphthyl phenyl ketones having a phenylthiyl moiety as a leaving group, p-(alpha-naphthoyl)benzyl phenyl sulfide (NBPS) and 4-benzoyl-1-naphthylmethyl phenyl sulfide (BNMPS), in solution were investigated by laser flash photolysis techniques. Both ketones were shown to undergo photoinduced omega-bond cleavage of the C-S bond to release the phenyl thiyl radical (PTR) at room temperature. Irrespective of excitation wavelengths of NBPS, a quantum yield (Phi(rad)) of the PTR formation was obtained to be 0.1, whereas that for BNMPS was found to depend on the excitation wavelength, i.e., absorption bands from the ground state (S0) to the excited singlet states, S3, S2, and S1 of BNMPS; Phi(rad)(S3) = 0.77 and Phi(rad)(S2) = Phi(rad)(S1) = 1.0. By using triplet sensitization of p-phenylbenzophenone (PBP), efficiencies (alpha(rad)) of the radical formation in the lowest triplet state (T1(pi,pi*)) of NBPS and BNMPS were determined to be 0 and 1.0, respectively. The agreement between Phi(rad)(S1) and alpha(rad) values for BNMPS indicates that the C-S bond dissociation occurs in the T1 state via the S1 state via a fast intersystem crossing from the S1 to the T1 state. The wavelength dependence of the radical yields upon direct excitation of BNMPS was interpreted in terms of the C-S bond cleavage in the S3 state competing with internal conversion from the S3 to the S2 state. The smaller value of Phi(rad)(S3) than those of Phi(rad)(S1) and Phi(rad)(S2) was proposed to originate from the geminate recombination of singlet radical pairs produced by the bond dissociation via the S3 state. Photoinduced omega-cleavage of NBPS was concluded to take place only in the S1(n,pi*) state. Difference in reactivity of omega-cleavage between the triplet states of NBPS and BNMPS was interpreted in terms of localized triplet exciton in the naphthoyl moieties.     

3-Band theory of Fe pnictide superconductors

For the Fe pnictide superconductors, band features important for superconductivity (SC) in the neighborhood of ε_F are mimicked by tight-binding bands with bases of Fe d_xz, d_yz and d_xy orbitals. In terms of this 3-band model, effective pair transfer processes originating from Coulombic integrals are shown to be largely enhanced due to the nesting between electron and hole pockets by explicitly summing up ladder diagrams. Obtained coupled gap equations lead to s^±-type SC. This framework are argued to provide a scheme for discussing important elements working for the high T_c SC, although its validity is restricted to the case where Dirac cones are away from ε_F. Experimental results on Fe pnictides are discussed in terms of the present results. The pair transfer process explicitly due to the exchange-like integral is suggested to be considerably important for the high T_c in MFeAsO_1−xF_x to occur.     

MOCVD growth of spherical aggregates of SiC nanocrystallites

Spherical aggregates of SiC nanocrystallites can be grown in addition to SiC nanowires via metal organic chemical vapor deposition using methylvinyldichlorosilane as a source gas and Ni catalyst by controlling the growth temperature and the pressure of the source gas. Electron microscopy observations show that the aggregates are typically 300 nm in diameter, which consist of SiC nanocrystallites of about 5 nm in diameter. Electron diffraction reveals that the nanocrystallites have the 3C structure.