Dual room-temperature fluorescent and phosphorescent emission in 8-quinolinolate osmium(II) carbonyl complexes: rationalization and generalization of intersystem crossing dynamics

A new series of quinolinolate osmium carbonyl complexes were synthesized and characterized by spectroscopic methods. Single-crystal X-ray diffraction studies indicate that these complexes consist of an octahedral ligand arrangement with one chelating quinolinolate, one tfa or halide ligand, and three mutually orthogonal terminal CO ligands. Variation of the substituents on quinolinolate ligands imposes obvious electronic or structural effects, while changing the tfa ligand to an electron-donating iodide slightly increases the charge density on the central osmium atom. These Os(II) complexes show salient dual emissions consisting of fluorescence and phosphorescence, the spectral properties and relaxation dynamics of which have been studied comprehensively. The results, in combination with the theoretical approaches, lead us to propose that the emission mainly originates from the quinolinolate pi pi* state. Both experimental and theoretical approaches generalize various types of intersystem crossing versus those of the tris(quinolinolate) iridium Ir(Q)3, and their relative efficiencies were accessed on the basis of the associated frontier orbital configurations. Our results suggest that [1d(pi)pi* absolute value(H(so))3 pi pi*] (or [3d(pi)pi* absolute value(H(so))1 pi pi*]) in combination with a smaller deltaE(S1-T1) gap (i.e., increasing the MLCT (d(pi)pi*) character) is the main driving force to induce the ultrafast S1 --> T1 intersystem crossing in the third-row transition metal complexes, giving the strong phosphorescent emission.     

Speciation of bound and free metals evaluated for lobster digestive gland extracts

A simple method is described for the speciation of metalions in biological extracts with a short desalting gel-filtration column. The system was optimized for the eluent and gel type to provide accurate free metal ion levels and minimum processing times. The four separation media studied were Sephadex G25, Bio-Gel P-6DG, controlled pore glass CPG40, and Fractogel HW40F. The best medium was the Fractogel HW40F because it was not compressible and allowed a pump to be used to obtain uniform flow rates. The eluent was 0.10 M ammonium acetate/0.01 M citric acid adjusted to pH 7.0. This eluent minimized ion/gel interactions and gave a lower salt content relative to other possible eluents. The separation time was 10 min per sample per metal ion of interest. The detection limits relative to the mass of wet tissue for the column/flame spectrometer system were 0.80 μg g^?1, 0.80 μg g^?1, and 1.6 μg g^?1 for zinc, cadmium and copper, respectively. The method is evaluated for a lobster digestive gland extract; the methodology should be applicable to other systems containing nonlabile metal species.     

Effects of Different Extraction Methods on Vanilla Aroma

To establish the analytic conditions for examining the aroma quality of vanilla pods, we compared different extraction methods and identified a suitable option. We utilized headspace solid-phase microextraction (HS-SPME), steam distillation (SD), simultaneous steam distillation (SDE) and alcoholic extraction combined with gas chromatography (GC) and gas chromatography–mass spectrometry (GC-MS) to identify volatile components of vanilla pods. A total of 84 volatile compounds were identified in this experiment, of which SDE could identify the most volatile compounds, with a total of 51 species, followed by HS-SPME, with a total of 28 species. Ten volatile compounds were identified by extraction with a minimum of 35% alcohol. HS-SPME extraction provided the highest total aroma peak areas, and the peak areas of aldehydes, furans, alcohols, monoterpenes and phenols compounds were several times higher than those of the other extraction methods. The results showed that the two technologies, SDE and HS-SPME, could be used together to facilitate analysis of vanilla pod aroma.     

Orthogonal carbazole-perylene bisimide pentad:a photoconversion-tunable photosensitizer with diversified excitation and excited-state relaxation pathways

Integrating multiple photosensitive properties into an "all-in-one" photosensitizer (PS) shows great promise for the treatment of cancers owing to synergistic e...     

Spectroscopy and femtosecond dynamics of 7-N,N-diethylamino-3-hydroxyflavone. The correlation of dipole moments among various states to rationalize the excited-state proton transfer reaction

Comprehensive excitation behaviors of 7-N,N-diethylamino-3-hydroxyflavone (I) have been investigated via steady state, temperature-dependent emission, and fluorescence upconversion to probe the excited-state intramolecular proton transfer (PT) reaction. Upon excitation, I undergoes ultrafast (<120 fs), adiabatic type of charge transfer (CT), so that the dipolar vector in the Franck-Condon excited state is much different from that in the ground state. In polar solvents such as CH2Cl2 and CH3CN, early relaxation dynamics clearly reveals the competitive rates between solvent relaxation and PT dynamics. After reaching thermal equilibrium, a relatively slow, solvent-polarity-dependent rate (a few tens of picoseconds(-1)) of PT takes places. Firm support of the early relaxation dynamics is rendered by the spectral temporal evolution, which resolves two distinct bands ascribed to CT and PT emission. The results, in combination with ab initio calculations on the dipolar vectors for various corresponding states, led us to conclude that excited-state normal (N*) and excited proton-transfer tautomer (T*) possesses very different dipole orientation, whereas the dipole orientation of the normal ground state (N) is between that of N* and T*. PT is thus energetically favorable at the Franck-Condon excited N*, and its rate is competitive with respect to the solvent relaxation dynamics induced by CT. Unlike the well-known PT system, 4'-N,N-diethylamino-3-hydroxyflavone, in which equilibrium exists between solvent-equilibrated N(eq)* and T(eq)*, N(eq)* --> T(eq)* PT for I is a highly exergonic, irreversible process in all solvents studied. Further temperature-dependent studies deduce a solvent-polarity-perturbed energy barrier of 3.6 kcal/mol for the N(eq)* --> T(eq)* PT in CH3CN. The proposed dipole-moment-tuning PT mechanism with the associated relaxation dynamics is believed to apply to many PT molecules in polar, aprotic solvents.     

A theoretical investigation of low energy band gap polymers: polythiophene systems

Recently, the organic synthesis and electronic device applications of π-conjugated polymer-based materials with low energy band gap (below 2 eV) and high values of incident photon to current efficiency have been presented. In the present study, the physical properties of polythiophene (PTH) and its derivative systems (PTs) were investigated as π-conjugated low energy band gap polymers. Density functional theory with periodic boundary condition (PBC), the B3LYP functional, and the 6-31G(d) basis set was applied to determine their geometric and electronic structures and corresponding energies (E _HOMO, E _LUMO, and E _g = E _LUMO ? E _HOMO) from the monomer of thiophene and its derivatives for one-dimensional (1D) extension to polymer. The effects of 3-substitution in PTs including electron-donating (CH₃–, C₆H₁₃–, OH–, Cl–, OCH₃–, and CHO–) and electron-withdrawing groups (Cl–, CHO–, CN–, NO₂–, CF₃–, and COOH–) compared with PTH were investigated. According to the calculation results, PTs with electron-donating and electron-withdrawing substituents should exhibit red- and blue-shifts, respectively, compared with PTH. These calculation results show good agreement with experimental data and provide further information for molecular design considerations.     

KNSBN晶体猫式互抽运相位共轭光特性

在KNSBN∶Ce晶体中,利用二波耦合作用,在单一光束无法获得相位共轭光的条件下,实现了“猫”式互抽运相位共轭光输出,获得较高的共轭光反射率.实验结果表明,晶体的二波耦合作用可以使晶体的自抽运相位共轭光的阈值光强降低、入射光的入射角范围增大、响应时间缩短 关键词： 钾钠铌酸锶钡晶体 互抽运相位共轭 二波耦合 自抽运相位共轭 响应时间     

A mechanistic study of flame retardance of novel copolyester phosphorus containing linked pendant groups by TG/XPS/direct Py-MS

The flame retardant mechanism of the copolyester phosphorus containing linked pendant groups was investigated by thermogravimetric （TG）, X-ray photoelectron spectroscopy （XPS） and direct insertion probe pyrolysis mass spectrometry （DP-MS） technique. TG results show that the incorporation of phosphorus containing unit linked pendant groups can destabilize the copolyester due to the cleavage of P-CH2 bond, and phosphorus containing units cannot promote the char-formation of the copolyester during the thermal degradation of the copolyester. XPS spectra indicate that with the increase of the temperature, the P-CH2 bonds of the copolyester break down gradually, the concentration of phosphorus in the condensed phase products decrease gradually and the chemical state of phosphorus does not change in the temperature of 250-380 ℃. Direct pyrolysis MS suggests that the P-CH2 bonds cleavage occurs at pendant groups and species containing phosphorus can volatilize into the gas phase. A flame retardant mechanism is proposed for the gas phase mode of action of the halogen-free copolyester phosphorus containing linked pendant groups.