Luminescent organoplatinum(II) complexes with functionalized cyclometalated C^N^C ligands: structures, photophysical properties, and material applications

A series of [(R'-C^N^C-R')Pt(L)] complexes with doubly deprotonated cyclometalated R'-C^N^C-R' ligands (R'-C^N^C-R'=2,6-diphenylpyridine derivatives) functionalized with carbazole, fluorene, or thiophene unit(s) have been synthesized and their photophysical properties studied. The X-ray crystal structures reveal extensive intermolecular π···π and C-H···π interactions between the cyclometalated C^N^C ligands. Compared to previously reported cyclometalated platinum(II) complexes [(C^N^C)Pt(L)], which are non-emissive in solution at room temperature, the carbazole-, fluorene- and thiophene-functionalized [(R'-C^N^C-R')Pt(L)] (L=DMSO 1-9, C≡N-Ar, 1a-9a) complexes are emissive in solution at room temperature with λ(max) at 564-619 nm and Φ=0.02-0.26. The emissions of the [(R'-C^N^C-R')Pt(L)] complexes are attributed to electronic excited states with mixed (3)MLCT and (3)IL character. The carbazole/fluorene/thiophene unit(s) allow the tuning of the electronic properties of the [(R'-C^N^C-R')Pt] moiety, with the emission maxima in a range of 564-619 nm. These are the first examples of organoplatinum(II) complexes bearing doubly deprotonated cyclometalated C^N^C ligands that are emissive in solution at room temperature. In non-degassed DMSO, the emission intensities of 6a-9a are enhanced upon exposure to ambient light. This phenomenon is caused by reacting photogenerated (1)O(2) with a DMSO molecule to form dimethyl sulfone, leading to the removal of dissolved oxygen in solution. Self-assembled nanowires and nanorods are obtained from precipitation of 3a in THF/H(2)O and 8a in DMSO/Et(2)O, respectively. The [(R'-C^N^C-R')Pt(L)] complexes are soluble in common organic solvents with a high thermal stability (>300 °C), rendering them as phosphorescent dopants for organic light-emitting diode (OLEDs) applications. Red OLEDs with CIE coordinates of (0.65±0.01, 0.35±0.01) were fabricated from 7a or 8a. A maximum external efficiency (η(Ext)) of 12.6% was obtained for the device using 8a as emitter.     

Enantiotropic Nematics From Cross‐Like 1,2,4,5‐Tetrakis(4′‐alkyl‐4‐ethynylbiphenyl)benzenes and Their Biaxiality Studies

The theoretically predicted optimum length/breadth/width ratio for maximizing shape biaxiality was investigated experimentally by the facile and successful synthesis of cross‐shaped compound 3 , which showed enantiomeric nematic phase behavior. This cross‐like core structure could alternatively be viewed as two fused V‐shaped mesogens, which have recently immerged as a new direction in biaxial nematic research, at the bending tips that can act as a new structure for biaxial investigations. Whilst the thermal analysis data of compound 3 did not meet the expected theoretical values for biaxial nematics, surface‐induced biaxiality was evidenced by optical studies. Cluster‐size analysis within the nematic phase of compound 3 revealed the formation of meta‐cybotactic nematics, which approached the cluster sizes of cybotactic nematics. The split small‐angle 2D X‐ray diffraction patterns of magnetic‐field‐aligned samples indicated that the nematic phase was composed of small smectic C‐like clusters with the tilting of molecules within the clusters. The wide‐temperature‐range enantiomeric nematic phase of cross‐like compound 3 enabled the molecular skeleton to serve as an alternative skeleton to bent‐rod mesogens, which exhibited nematic phases with the potential competition of transitions to higher‐order liquid‐crystalline phases and crystallization, for future biaxial investigations.     

Chiral electrokinetic chromatography-electrospray ionization-mass spectrometry using a double junction interface

A double junction interface was utilized to preserve separation efficiency and alleviate ion suppression from sulfated β-cyclodextrin (S-β-CD) in electrokinetic chromatography-electrospray ionization-mass spectrometry. The utility of the approach was demonstrated by chiral EKC-MS analysis of dihydroxyphenylalanine and methyldihydroxyphenylalanine enantiomers using either low concentration (counter-migration mode; 0.1% S-β-CD) or high concentration (carrier mode; 2% S-β-CD). In the counter-migration mode, S-β-CD anions were supplied continuously from the junction reservoir to the separation column so that the effective separation length was preserved. This interface is especially useful under carrier mode in which high concentration of S-β-CD will migrate toward the ESI source. With the use of the double junction interface, the S-β-CD exited the separation column will remain in the junction reservoir, whereas the analyte will flow toward the ESI source through a connecting column. As a result, no ion suppression was observed and the sensitivity was improved significantly.     

Determination of the Navier slip coefficient of microchannels exploiting the streaming potential

For most microchannels made of hydrophobic materials such as polymers, velocity slip occurs at the wall, affecting volumetric flow rate of electroosmotic flow Q(eof) and streaming potential (??(str)/?z). Since most techniques exploit Q(eof) or (??(str)/?z) to determine the zeta potential, ζ, it is very difficult to measure ζ of hydrophobic walls, if the slip coefficient b is not found a priori. Until now, Q(eof) and (??(str)/?z) are known to depend on ζ and b in a same functional form, which makes it impossible to estimate ζ or b separately using measurements of Q(eof) and (??(str)/?z). However, exploiting the analytic formula for Q(eof) and (??(str)/?z) derived in the present work, it is found that the effect of ζ and that of b on Q(eof) and (??(str)/?z) can be separated from each other by varying the bulk ionic concentration. Thus, the slip coefficient as well as the zeta potential of hydrophobic microchannels can be found with reasonable accuracy by means of a nonlinear curve fitting method using measured data of Q(eof) and (??(str)/?z) at various bulk ionic concentrations. The present method allows an accurate estimation of slip coefficient of hydrophobic microchannels, which is quite simple and cheap compared with methods employing microparticle velocimetry.     

Superior dispersion of highly reduced graphene oxide in N,N-dimethylformamide

Here, we report the effect of temperature on the extent of hydrazine reduction of graphene oxide in N,N-dimethylformamide (DMF)/water (80/20 v/v) and the dispersibility of the resultant graphene in DMF. The highly reduced graphene oxide (HRG) had a high C/O ratio and good dispersibility in DMF. The good dispersibility of HRGs is due to the solvation effect of DMF on graphene sheets during the hydrazine reduction, which diminishes the formation of irreversible graphene sheet aggregates. The dispersibility of the HRGs was varied from 1.66 to 0.38 mg/mL when the reduction temperature increased from 25 °C to 80 °C. The dispersibility of the HRGs was inversely proportional to the electrical conductivity of the HRGs, which varied from 17,400 to 25,500 S/m. The relationships between the C/O ratio, electrical conductivity, and dispersibility of the HRGs were determined and these properties were found to be easily controlled by manipulating the reduction temperature.     

Syntheses of Amino Group‐Substituted N‐Confused Porphyrins

Tetraphenyl N‐confused porphyrins (NCTPP) bearing amino substituents were synthesized for the purpose of functionalization toward water‐soluble and biocompatible molecules. The Pd‐catalyzed coupling reaction of 4‐ethynylaniline with the 2‐bromo NCTPP Ag(III) complex yields Pd(II) and Ag(III) coupling products ( 4a and 4b ), at 39% and 55%, respectively. The identities of these products were confirmed by the differences in the isotope patterns of their molecular ion peaks as well as other spectroscopic data. The Ag(III) coupling product, 4b , was demetallated to form the final product, 5 , with a yield of 85%. The meso‐tetrakis(4‐nitrophenyl) N‐confused porphyrin, 6 , was synthesized through a methanesulfonic acid catalyzed condensation of pyrrole with the 4‐nitrobenzaldehyde with a yield of 6.8%. Reduction of the compound to meso tetrakis(4‐aminophenyl) N‐confused porphyrin, 7 , was achieved with a yield of 90%.     

Polarized Laser Raman Spectra of the Crystal Cs3UO2F3

Abstract

Polarized Raman spectra of Cs₃UO₂F₅ in which the UO₂F₅ ^3? ion is in its statistical position have made it possible to assign definitely the Raman fundamental vibration modes as follows : v₁(A′¹) = 784, v₂(A′¹) = 423, v₈(E′²) = 325, v₈(E′²) = 219 and v₁₀(E″¹) = 259 cm^?1.     

Comparison of the LMCT resonance Raman spectra of PdCl2(PCy3)2 and PdCl2(PPh3)2: effect of the phenyl versus cyclohexyl substituents on the LMCT excited state

Resonance Raman spectra have been obtained at four excitation wavelengths within the A-band ligand to metal charge transfer (LMCT) absorption of trans-dichloro-bis(tricyclo-hexylphosphine) palladium(II) and a resonance Raman intensity analysis was done to elucidate the excited state structure relative to the ground state. Comparison of the present results for trans-dichlorobis(tricyclohexylphosphine) palladium(II) with those previously reported for trans-dichlorobis(triphenylphosphine) palladium(II) shows that the phenyl ligand appears to primarily affect the adjacent P-C vibrational reorganizational energy and does not significantly perturb the Pd-Cl or Pd-P vibrational reorganizational energies.     

Contour estimation via two fidelity computer simulators under limited resources

The utilization of multiple fidelity simulators for the design and analysis of computer experiments has received increased attention in recent years. In this paper, we study the contour estimation problem for complex systems by considering two fidelity simulators. Our goal is to design a methodology of choosing the best suited simulator and input location for each simulation trial so that the overall estimation of the desired contour can be as good as possible under limited simulation resources. The proposed methodology is sequential and based on the construction of Gaussian process surrogate for the output measure of interest. We illustrate the methodology on a canonical queueing system and evaluate its efficiency via a simulation study.     

Normal Restriction in Finite Groups

A subgroup H of a finite group G is called an NR ? subgroup (Normal Restriction) if whenever K ? H, then K ^G ∩ H = K, where K ^G is the normal closure of K in G. In this article, we will prove some sufficient conditions for the solvability of finite groups which possess many NR-subgroups. We also prove a criterion for the existence of a normal p-complement in finite groups.