Bandgap engineering of indenofluorene‐based conjugated copolymers with pendant donor‐π‐acceptor chromophores for photovoltaic applications

Three narrow‐band‐gap conjugated copolymers based on indenofluorene and triphenylamine with pendant donor‐π‐acceptor chromophores were successfully synthesized by post‐functionalization approach. All the polymers have good solubility in common solvents and excellent thermal stability. The photophysical properties, energy levels and band gaps of the polymers were well manipulated by introducing different acceptor groups onto the end of their conjugated side chains. By using different acceptor groups, the band gaps of the polymers were narrowed from 1.86 to 1.53 eV by lowering their lowest unoccupied molecular orbital levels, whereas their relatively deep highest occupied molecular orbital levels of approximately ?5.35 eV were maintained. Bulk‐heterojunction solar cells with these polymers as electron donors and (6,6)‐phenyl‐C₇₁‐butyric acid methyl ester as acceptor showed power conversion efficiencies as high as 3.1% and high open circuit voltages more than 0.88 eV. The relationships between the performance and film morphology, energy levels, charge mobilities were discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Quantification of Photosensitized Singlet Oxygen Production by a Fluorescent Protein

Fluorescent proteins are increasingly becoming actuators in a range of cell biology techniques. One of those techniques is chromophore‐assisted laser inactivation (CALI), which is employed to specifically inactivate the function of target proteins or organelles by producing photochemical damage. CALI is achieved by the irradiation of dyes that are able to produce reactive oxygen species (ROS). The combination of CALI and the labelling specificity that fluorescent proteins provide is useful to avoid uncontrolled photodamage, although the inactivation mechanisms by ROS are dependent on the fluorescent protein and are not fully understood. Herein, we present a quantitative study of the ability of the red fluorescent protein TagRFP to produce ROS, in particular singlet oxygen (¹O₂). TagRFP is able to photosensitize ¹O₂ with an estimated quantum yield of 0.004. This is the first estimation of a quantum yield of ¹O₂ production value for a GFP‐like protein. We also find that TagRFP has a short triplet lifetime compared to EGFP, which reflects relatively high oxygen accessibility to the chromophore. The insight into the structural and photophysical properties of TagRFP has implications in improving fluorescent proteins for fluorescence microscopy and CALI.     

The Effect of the Buffering Capacity of the Supporting Electrolyte on the Electrochemical Oxidation of Dopamine and 4‐Methylcatechol in Aqueous and Nonaqueous Solvents

Dopamine was electrochemically oxidized in aqueous solutions and in the organic solvents N,N‐dimethyl‐formamide and dimethylsulfoxide containing varying amounts of supporting electrolyte and water, to form dopamine ortho‐quinone. It was found that the electrochemical oxidation mechanism in water and in organic solvents was strongly influenced by the buffering properties of the supporting electrolyte. In aqueous solutions close to pH 7, where buffers were not used, the protons released during the oxidation process were able to sufficiently change the localized pH at the electrode surface to reduce the deprotonation rate of dopamine ortho‐quinone, thereby slowing the conversion into leucoaminochrome. In N,N‐dimethylformamide and dimethylsulfoxide solutions, in the absence of buffers, dopamine was oxidized to dopamine ortho‐quinone that survived without further reaction for several minutes at 25 °C. The voltammetric data obtained in the organic solvents were made more complicated by the presence of HCl in commercial sources of dopamine, which also underwent an oxidation process.     

A Highly Sensitive and Recyclable Ln‐MOF Luminescent Sensor for the Efficient Detection of Fe3+ and CrVI Anions

Two new three‐dimensional (3D) Ln^III metal‐organic frameworks (MOFs) were designed and successfully obtained via a solvothermal reaction between lanthanide(III) nitrates and a semi‐flexible carbazole tetracarboxylate acid linker as a high‐performance chromophore. 1 and 2 possess porous 3D networks with channels along the a axis, and more importantly, they show a highly sensitive and selective fluorescence quenching response to Fe³⁺ and Cr^VI anions. The sensing mechanism investigation revealed that the weak interactions of Fe³⁺ with nitrogen atoms of carbazole and deprotonated carboxylic acids protruding into the pores of MOFs quenched the luminescence of 1 and 2 effectively. In addition, the competition absorption also played an important role in the luminescence quenching detection of Fe³⁺ based on 1 , and Cr^VI anions based on 1 and 2 . Therefore, 1 and 2 represent an alternative example of regenerable luminescence based sensors for the quantitative detection of Fe³⁺ and Cr^VI anions.     

含呋喃共轭桥有机非线性光学生色团的合成及性能研究

通过两次羟醛缩合反应合成了一种含呋喃共轭桥的有机非线性光学生色团分子2-二氰亚甲基-3-氰基-4-[2-(4-二乙氨基-苯乙烯基-呋喃基-5)-乙烯基]-5,5-二甲基-2,5-二氢呋喃(EFFC), 用IR谱、¹H NMR谱以及元素分析表征确认了其结构. 热失重分析表明, 材料的热分解温度T_d为250℃. 用密度泛函理论的B3LYP方法在6-31G基组下对这种生色团分子进行了结构优化, 并在相同基组下对分子的静态二阶极化率进行了计算, 分子的b₀=6.5×10^-28 esu. 将分子以18%的质量比与聚砜进行主-客体掺杂, 用溶胶凝胶法制备成膜后进行极化, 用二次谐波法对掺杂极化聚合物薄膜的电光系数进行测量, 其r₃₃值最高达到80 pm/V.     

Spectroscopic Properties and Three-photon Absorption Induced Optical Limiting of Series of Novel Nonlinear Chromophores

Three novel nonlinear chromophores with symmetric D-π-D molecular structure and extended conjugated length were synthesized. Solvatochromism analysis shows great symmetric intramolecular charge transfer occurring in chromophores by the enhancement in the dipole moment between the ground and excited states. The properties of optical power limiting induced by three-photon absorption (3PA) are demonstrated. Large 3PA coefficients and the corresponding molecular cross sections as high as 10-74 cm6s2 were obtained for nanosecond laser pulses at 1.06 μm from nonlinear transmission measurements.     

Electro‐Optic (E‐O) Molecular Glasses

This Focus Review describes molecular glasses as a new class of materials for nonlinear optical (NLO) applications, especially for electro‐optic (E‐O) devices. Examples of E‐O molecular glasses are reviewed with a focus on the molecular design of NLO chromophores and solid‐state engineering of molecular glasses. Molecular glasses based on dendrimers of multiple chromophores, molecular glass blends of chromophores, and molecular glasses based on reversible self‐assembly of chromophores are introduced as promising architectures to prepare morphologically stable molecular glasses with large E‐O activities and improved material properties for device applications. Future directions to fully exploit the potential of molecular glasses for NLO materials are presented.