Polymorphic forms of a gold(I) arylacetylide complex with contrasting phosphorescent characteristics

The spectroscopic properties and crystal structures of the gold(I) arylacetylide complexes [(R(3)P)Au(Ctbd1;CAr)] (R = Cy, Ar = 4-nitrophenyl, 1; 4-trifluoromethylphenyl, 2; pentafluorophenyl, 3; R = Ph, Ar = 4-nitrophenyl, 4) have been examined. The dipole-allowed and -forbidden transitions of 1 (4 in parentheses) at lambda(max) 340 (336) and ca. 485 (470) nm in CH(2)Cl(2) solution at 298 K are assigned to the singlet and triplet intraligand charge transfer (ILCT) transitions of the 4-nitrophenylacetylide moiety, whereas 2 (3 in parentheses) shows localized singlet and triplet acetylenic pipi transitions at lambda(max) 287 (276) and 426 nm, respectively. Two polymorphs of 1 with contrasting phosphorescent characteristics have been identified. At 298 K, the emissive form of 1, as well as 2-4, are highly phosphorescent with peak maximum at 504, 425, 521, and 495 nm, respectively; the other polymorph of 1 is nonemissive at 298 K but emission is detected at 77 K with peak maximum at 486 nm. Crystallographic studies reveal that the major differences between the emissive and nonemissive forms of 1 are the orientations of the molecular dipoles and the dihedral angles between neighboring 4-nitrophenyl moieties. Crystal 2 is isostructural to the nonemissive form of 1, but does not display polymorphism. The molecular planes of two neighboring lumophores are coplanar in the emissive form of 1, parallel in 4, and nearly perpendicular (78.6 degrees ) to each other in the nonemissive form of 1. Both the nature of the excited state and the dihedral angle between adjacent [Au(Ctbd1;CAr)] moieties determine the phosphorescent properties of these molecular crystals.     

Reactivity of dioxoosmium(VI) porphyrins toward arylhydrazine. Isolation of hydrazidoosmium and amidoosmium porphyrins

Reactions of dioxoosmium(VI) porphyrins [Os(VI)(Por)O(2)] with excess 1,1-diphenylhydrazine in tetrahydrofuran at ca. 55 degrees C for 15 min afforded bis(hydrazido(1-))osmium(IV) porphyrins [Os(IV)(Por)(NHNPh(2))(2)] (1a, Por = TPP (meso-tetraphenylporphyrinato dianion); 1b, Por = TTP (meso-tetrakis(p-tolyl)porphyrinato dianion)), hydroxo(amido)osmium(IV) porphyrins [Os(IV)(Por)(NPh(2))(OH)] (2a, Por = TPP; 2b, Por = TTP), and bis(hydrazido(2-))osmium(VI) porphyrin [Os(VI)(Por)(NNPh(2))(2)] (3c, Por = TMP (meso-tetramesitylporphyrinato dianion)). The same reaction under harsher conditions (in refluxing tetrahydrofuran for ca. 1 h) gave a nitridoosmium(VI) porphyrin, [Os(VI)(Por)(N)(OH)] (4b, Por = TTP). Oxidation of 1a,b with bromine in dichloromethane afforded bis(hydrazido(2-)) complexes [Os(VI)(TPP)(NNPh(2))(2)] (3a) and [Os(VI)(TTP)(NNPh(2))(2)] (3b), respectively. All the new osmium porphyrins were identified by (1)H NMR, IR, and UV-vis spectroscopy and mass spectrometry; the structure of 2b was determined by X-ray crystallography (Os-NPh(2) = 1.944(6) A, Os-OH = 1.952(5) A).     

Functional-coefficient partially linear regression model

In this paper, the functional-coefficient partially linear regression (FCPLR) model is proposed by combining nonparametric and functional-coefficient regression (FCR) model. It includes the FCR model and the nonparametric regression (NPR) model as its special cases. It is also a generalization of the partially linear regression (PLR) model obtained by replacing the parameters in the PLR model with some functions of the covariates. The local linear technique and the integrated method are employed to give initial estimators of all functions in the FCPLR model. These initial estimators are asymptotically normal. The initial estimator of the constant part function shares the same bias as the local linear estimator of this function in the univariate nonparametric model, but the variance of the former is bigger than that of the latter. Similarly, initial estimators of every coefficient function share the same bias as the local linear estimates in the univariate FCR model, but the variance of the former is bigger than that of the latter. To decrease the variance of the initial estimates, a one-step back-fitting technique is used to obtain the improved estimators of all functions. The improved estimator of the constant part function has the same asymptotic normality property as the local linear nonparametric regression for univariate data. The improved estimators of the coefficient functions have the same asymptotic normality properties as the local linear estimates in FCR model. The bandwidths and the smoothing variables are selected by a data-driven method. Both simulated and real data examples related to nonlinear time series modeling are used to illustrate the applications of the FCPLR model.     

LOCAL MEDIAN ESTIMATION OF VARIANCE FUNCTION

This paper considers local median estimation in fixed design regression problems. The proposed method is employed to estimate the median function and the variance function of a heteroscedastic regression model. Strong convergence rates of the proposed estimators are obtained. Simulation results are given to show the performance of the proposed methods.     

(O--N--N)PtX] complexes as a new class of light-emitting materials for electrophosphorescent devices

The synthesis and photophysical properties of the robust Pt(II) emitters [(O--N--N)PtX] (HO--N--N = 6-(2-hydroxyphenyl)-2,2'-bipyridine and its derivatives; X = Cl, Br, I, or -CC-Ph) are reported. Yellow electroluminescent devices based on these materials display a low turn-on voltage (1 cd m(-2) at 4 V) and a high luminance (37000 cd m(-2)). Complex 2e, [(F(t)Bu2O--N--N)PtCl], has the highest thermal stability and gave the best OLED.     

Detection of CO using bulk ZnO Schottky rectifiers

Bulk Pt/ZnO Schottky rectifiers show gas sensitivities for CO of 4% and 8%, respectively, at 150 °C for 1 and 10% CO in N₂. The current or voltage changes are time dependent, with an activation energy of 40.7 kJmol^-1. Over a limited range of partial pressures of CO (P_CO) in the ambient gas, the on-state resistance R of the sensor at fixed bias voltage decreased according to R=(R_O+A(P_CO)^0.5)^-1, where A is a constant and R_O is the resistance in N₂. Since these devices are also sensitive to H₂ and C₂H₄, the ZnO rectifiers appear promising for a range of gas-sensing applications. PACS 81.05.Dz; 73.61.Ga; 72.80.Ey     

Fluorophore-appended steroidal saponin (dioscin and polyphyllin D) derivatives

The synthesis of three fluorophore-appended derivatives of dioscin and polyphyllin D is reported herein. Starting from trillin, dansyl derivatives A-C were prepared in overall yields of 7-12% over 7-10 steps. A study of their behavior in a variety of polar solvents suggests that dansyl derivatives A-C are capable of micellar self-assembly and can maintain cytotoxicities (IC50 = 15-18 muM) against the HeLa carcinoma cell line evaluated by standard MTT assay. [structure: see text]     

A J-multiplied HMQC (MJ-HMQC) experiment for measuring (3)J(HNHalpha) coupling constants

The J-multiplied HSQC experiment (MJ-HSQC: S. Heikkinen et al., J. Magn. Reson 137, 243 (1999)) amplifies J coupling constants m times and allows direct observation of the (3)J(HNHalpha) coupling constants of peptides and proteins (<10 kDa). The drawbacks to this method are line broadening in the f(1)-dimension and lower sensitivity. In the J-multiplied HMQC (MJ-HMQC) experiment described here, the PEP-HSQC pulse sequence is replaced by a sensitivity-enhanced HMQC section, and the total decay time for the J-coupling and the chemical shift evolution is shortened by a period of t(1). This experiment affords narrower linewidth and enhances the sensitivity by 34%, on an average of 105 well-isolated peaks, when compared with the MJ-HSQC experiment.