Highly phosphorescent iridium complexes containing both tridentate bis(benzimidazolyl)-benzene or -pyridine and bidentate phenylpyridine: synthesis, photophysical properties, and theoretical study of Ir-bis(benzimidazolyl)benzene complex

Novel mixed-ligand Ir(III) complexes, [Ir(L)(NwedgeC)X]n+ (L = N/\C/\N or N/\N/\N; X = Cl, Br, I, CN, CH3CN, or -CCPh; n = 0 or 1), were synthesized, where N/\CwedgeN = bis(N-methylbenzimidazolyl)benzene (Mebib) and bis(N-phenylbenzimidazolyl)benzene (Phbib), N/\N/\N = bis(N-methylbenzimidazolyl)pyridine (Mebip), and N/\C = phenylpyridine (ppy) derivatives. The X-ray crystal structures of [Ir(Phbib)(ppy)Cl] and [Ir(Mebib)(mppy)Cl] [mppy = 5-methyl-2-(2'-pyridyl)phenyl] indicate that the nitrogen atom of the ppy ligand is located trans to the coordinating carbon atom in Me- or Phbib, while the coordinating carbon atom in ppy occupies the trans position of Cl. [Ir(Mebip)(ppy)Cl]+ showed a quasireversible Ir(III/IV) oxidation wave at +1.05 V, while the Ir complexes, [Ir(Mebib)(ppy)Cl], were oxidized at +0.42 V versus Fc/Fc+. The introduction of an Ir-C bond in [Ir(Mebib)(ppy)Cl] induces a large potential shift of 0.63 V in a negative direction. Further, the oxidation potential of [Ir(Mebib)(Rppy)X] was altered by the substitution of R, R', and X groups. Compared to the oxidation potential, the first reduction potential revealed an almost constant value at -2.36 to -2.46 V for [Ir(L)(ppy)Cl] (L = Mebib and Phbib) and -1.52 V for [Ir(Mebip)(ppy)Cl. The UV-vis spectra of [Ir(Mebib)(R-ppy)X] show a clear singlet metal-to-ligand charge-transfer transition around 407 approximately 425 nm and a triplet metal-to-ligand charge-transfer transition at 498 approximately 523 nm. [Ir(Mebip)(ppy)Cl]+ emits at 610 nm with a luminescent quantum yield of Phi = 0.16 at room temperature. The phosphorescence of [Ir(Mebib)(ppy)X] was observed at 526 nm for X = CN and 555 nm for X = Cl with the high luminescent quantum yields, Phi = 0.77 approximately 0.86, at room temperature. [Ir(Phbib)(ppy)Cl] shows the emission at 559 nm with a luminescent quantum yield of Phi = 0.95, which is an unprecedentedly high value compared to those of other emissive metal complexes. Compared to the luminescent quantum yields of the Ir(ppy)2(L) derivatives and [Ir(Mebip)(ppy)Cl]+, the neutral Ir complexes, [Ir(L)(R-ppy)X] (L = Me- or Phbib), reveal very high quantum yields and large radiative rate constants (kr) ranging from 3.4 x 10(5) to 5.5 x 10(5) s(-1). The density functional theory calculation suggests that these Ir complexes possess dominantly metal-to-ligand charge-transfer and halide-to-ligand charge-transfer excited states. The mechanism for a high phosphorescence yield in [Ir(bib)(ppy)X] is discussed herein from the perspective of the theoretical consideration of radiative rate constants using perturbation theory and a one-center spin-orbit coupling approximation.     

Development of dual gradient column in liquid chromatography

The dual gradient column, in which both the chemical property of the stationary phase and the flow velocity in the mobile phase are heterogeneous longitudinally along the column, is developed to obtain the mobile phase gradient-like elution in an isocratic condition. Here, the step-wise dual gradient columns were prepared by connecting an inlet column (I.D. 50 microm, packed with ODS) serially to an outlet column (I.D. 100-200 microm, packed with the mixture of ODS and C1 [9:1]). The retention behavior of alkylbenzenes was able to be controlled in the dual gradient column depending on the variation in the flow velocity. Moreover, the change in retention behavior induced by the flow velocity variation for the dual gradient columns was quite different from that by the variation in organic modifier content of the mobile phase in isocratic elution for a single gradient column and can induce the similar effect with an ordinary gradient elution in a mobile phase composition.     

Orientational control of guest molecules in an organic intercalation system by host polymer tacticity

Four kinds of stereoregular poly(muconic acid)s, which are synthesized by topochemical polymerization and subsequent solid-state hydrolysis, are used as the organic host materials for intercalation. We describe the reaction behavior and layered structure of intercalation compounds using stereoregular poly(muconic acid)s and n-alkylamines as host and guest, respectively. The packing structure of the guest alkylamines was determined by X-ray diffractions as well as IR and Raman spectroscopies. We have found that the orientation of the guest molecules is controlled by the host polymer tacticity, depending on the structure of the two-dimensional hydrogen-bonding network formed in the polymer sheets of the crystals.     

Chemistry of anthracene-acetylene oligomers: synthesis and enantiomeric resolution of a chiral 1,8-anthrylene-ethynylene cyclic tetramer

To construct a new type of chiral pi-conjugated system, the title anthracene-acetylene oligomer containing two octyl groups at position 10 of 1,2-alternating anthracene groups was synthesized. Each anthracene unit was connected by Sonogashira coupling, and the tetrameric precursor was cyclized by a cross-coupling reaction to form the desired C2-symmetric compound. Its enantiomers were resolved by chiral HPLC with a Chiralcel OD column, and the chiroptical properties were investigated by optical rotation ([alpha]D(23) = -95 and +91) and circular dichroism (CD) measurements. The structural and spectroscopic features of this oligomer were discussed in terms of the molecular symmetry and the dynamic behavior of the macrocyclic framework.     

Palladium-catalyzed borylation of l-tyrosine triflate derivative with pinacolborane: practical route to 4-borono-l-phenylalanine (l-BPA) derivatives

Efficient palladium-catalyzed borylation of protected l-tyrosine triflate with pinacolborane was achieved despite previous reports to the contrary. In addition to the use of an inexpensive boron source, the reaction was carried out in the presence of only 0.5 mol % palladium catalyst. Furthermore, the borylation can be performed using pinacolborane prepared in situ from pinacol and borane-diethylaniline complex. This represents a practical entry to 4-borono-l-phenylalanine (l-BPA) derivatives.     

Temperature estimation in a ferromagnetic Fe-Ni nanowire involving a current-driven domain wall motion

We observed a magnetic domain wall (DW) motion induced by the spin-polarized pulsed current in a nanoscale Fe(19)Ni(81) wire using a magnetic force microscope. High current density, which is of the order of 10(11) A m(-2), was required for the DW motion. A simple method to estimate the temperature of the wire was developed by comparing the wire resistance measured during the DW motion with the temperature dependence of the wire resistance. Using this method, we found the temperature of the wire was proportional to the square of the current density and became just beneath at the threshold Curie temperature. Our experimental data qualitatively support this analytical model that the temperature is proportional to the resistivity, thickness, width of the wire and the square of the current density, and also inversely proportional to the thermal conductivity.     

Natural frequencies and vibration modes of laminated composite plates reinforced with arbitrary curvilinear fiber shape paths

The development of tow-placement technology has made it possible to control fiber tows individually and place fibers in curvilinear distinct paths in each layer of a laminated plate. This paper presents an analytical method for determining natural frequencies and vibration modes of laminated plates having such curvilinear reinforcing fibers. Spline functions are employed to represent arbitrarily shaped fibers, and Ritz solutions are used to derive frequency equations using series type shape functions. The strain energy is evaluated by numerical integration involving the fiber orientation angle, and is calculated using the derivative of the spline function in minute intervals. The results show that the natural frequencies obtained by the present method agree well with results from finite element analyses. The vibration mode shape contour plots of the plates are seen to reflect clear influences of the fiber shapes.     

A calorimetric study of the acid dissociation of the conjugate acids of poly(N-vinylimidazole) and polyallylamine

Thermodynamic parameters for acid dissociation of the conjugate acids of poly(N-vinylimidazole) and polyallylamine have been determined in the presence of sodium chloride and sodium nitrate. Even though the plots of ΔG ⁰ against the degree of dissociation, α, are highly dependent on the added salt concentration levels, the concentration effect has never been observed for the corresponding ΔH ⁰ versus α plots. The effect on the ΔG ⁰ versus α plots has been attributed to the entropy change of the counterions between a polyelectrolyte phase and a bulk solution phase. The α dependency of ΔH ⁰ is affected remarkably by the kinds of cationic polymers and counter-anions. Each ΔH ⁰ value at completely neutralized conditions is quite close to the corresponding ΔH ⁰ value of the monomer analog. The difference in the ΔH ⁰ values at fully charged conditions has been explained by the heats due to The ion-pair formation of chloride anion to the conjugate acids of poly(N-vinylimidazole) and polyallylamine has been supported by ³⁵Cl NMR measurement. It has also been suggested that chloride anions bind the basic polymer molecules even at fully neutralized conditions. Received: 2 June 1999/Accepted in revised form: 19 July 1999     

Stationary Waves for the Discrete Boltzmann Equation in the Half Space with Reflective Boundaries

The present paper is concerned with stationary solutions for discrete velocity models of the Boltzmann equation with reflective boundary condition in the first half space. We obtain a sufficient condition that guarantees the existence and the uniqueness of stationary solutions satisfying the reflective boundary condition as well as the spatially asymptotic condition given by a Maxwellian state. First, the sufficient condition is obtained for the linearized system. Then, this result is applied to prove the existence theorem for the nonlinear equation through the contraction mapping principle. Also, it is shown that the stationary solution approaches the asymptotic Maxwellian state exponentially as the spatial variable tends to infinity. Moreover, we show the time asymptotic stability of the stationary solutions. In the proof, we employ the standard energy method to obtain a priori estimates for nonstationary solutions. The exponential convergence at the spatial asymptotic state of the stationary solutions gives essential information to handle some error terms. Then we discuss some concrete models of the Boltzmann type as an application of our general theory. Received: 7 July 1999 / Accepted: 3 November 1999