Synthesis and nonlinear optical properties of branched pyrroline chromophores

New tricyanopyrroline (TCP) chromophores with rigid–flexible dendron were prepared for second‐order nonlinear optical (NLO) application. The chromophores were fully characterized using ultraviolet‐visible spectroscopy, nuclear magnetic resonance spectroscopy and mass spectrometry. Thermal gravimetric analysis (TGA) revealed that the chromophores had excellent thermal stability. Large λ_max and high solvate chromic effects revealed that the chromophores had large second‐order optical nonlinearity. The electro‐optic coefficients (r₃₃) were measured in the chromophores‐doped poly(bisphenol A carbonate) films at the fundamental wavelength of 1310 nm, and the highest γ₃₃ achieved was 217 pmV^?1. Copyright © 2010 John Wiley & Sons, Ltd.     

三枝加盖树状分子的一阶超极化率的理论研究

利用密度泛函理论计算了一系列三枝加盖树状发光分子的性质．发现加盖树状分子的二阶非线性光学性质和三支发色团的相对位置,所加盖子的数量,以及发色团的长度关系很大．当树状分子三枝的偶极矩平行度较高时,可以得到增强的一阶超极化率.     

有机二阶非线性光学发色团的研究进展

近年来,科学家们通过引进杂环片段、采用双(或多)官能化以及运用分子间弱相互作用等方法,在二阶非线性光学发色团的性能优化方面取得了较大进展.结合本课题组的研究,对此领域的研究进行了较全面的综述,并特别针对“非线性-透光性”矛盾的解决途径进行了较为详细的介绍.     

Red‐Shifted Fluorescent Aminated Derivatives of a Conformationally Locked GFP Chromophore

A novel class of fluorescent dyes based on conformationally locked GFP chromophore is reported. These dyes are characterized by red‐shifted spectra, high fluorescence quantum yields and pH‐independence in physiological pH range. The intra‐ and intermolecular mechanisms of radiationless deactivation of ABDI‐BF2 fluorophore by selective structural locking of various conformational degrees of freedom were studied. A unique combination of solvatochromic and lipophilic properties together with “infinite” photostability (due to a dynamic exchange between free and bound dye) makes some of the novel dyes promising bioinspired tools for labeling cellular membranes, lipid drops and other organelles.     

Properties of Some Polarized Chromophores in Polyvinylpyrrolidone

Poor miscibility of highly polarized chromophores to polymer matrices is a crucial issue for EO polymer development. By using poly(N-vinylpyrrolidone) (PVP) as a matrix polymer, we were able to prepare the uniform film containing ammonium-borate type zwitterions or Disperse Red 1 (DR1). For zwitterions, corona poling was unsuccessful probably because of hygroscopic property of PVP and/or strong intermolecular interaction to form the antiparallel dimers. For DR1, we found apparent color change originated from the H-aggregate formation assisted by moisture, which is usable to detect humidity. On the other hand, a passivation layer is necessary to use PVP for the EO applications.     

Retinal in bacteriorhodopsin and related molecular models investigated with Raman spectroscopy and density functional theory calculations

A first‐principles assisted study of the Raman spectrum associated with the photoactive chromophore in bacteriorhodopsin (bR) allowed the elucidation of the effective coupling existing between the π electrons of the retinylidene chromophore and the local environment of the Schiff base. The role of the counter‐ion on the electronic and vibrational structure of the chromophore is investigated by means of density functional theory (DFT) calculations. Several molecular models of the retinylidene chromophore interacting with different counter‐ions facing the Schiff base have been considered. The counter‐ion induces a strong modulation of the position of both the UV–vis absorption maximum and the strong Raman active collective CC stretching mode, related to the effective conjugation coordinate (ECC). Experimental Raman and UV–vis absorption data are interpreted in the light of these theoretical findings. The data collected in this paper provide an interesting accumulation of points along the optical gap versus ECC wavenumber relationship. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis,structure and nonlinear optical properties of two novel two-photon absorption chromophores

Two triphenylamine-based derivatives that can be used as two-photon absorption chromophore,tris{4-[4-(3-trifluoromethyl-3-oxopanoyl)]phenyl}amine (1) and tris{4-[4-(3-phenyl-3-oxopanoyl)] phenyl} amine (2) were successfully synthesized and fully characterized by elemental analysis,IR,1H NMR and MS. The single crystal X-ray diffraction analysis showed that the molecules possess D-(π-A)3 structures. One-and two-photon absorption and fluorescence in various solvents were experimentally investigated. A data rec...     

Synthesis and Nonlinear Optical Properties of Chromophores with 1,8-Dimethoxy-9,10-dihydroanthracene and Ring-locked Triene

The new chromophore molecules with nonlinear optical （NLO） properties were prepared by Knoevenagel condensation from 1,8-dimethoxy-4,5-diformyl-9,10-dihydroanthracene and isophorone derivative in the presence of piperidine and acetic acid. In these chromophore, the ring-locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The key intermediate dialdehyde was conveniently prepared via a three step reaction, in which 1,8-dimethoxyanthraquinone was reduced with zinc/acetic acid and sodium/ethanol successively, followed by formylation with 1,1-dichlorodimethyl ether in the presence of TiCI4. The solvatochromism and UV spectra indicate that they have higher second-order nonlinear hyperpolarizability μβ values than the corresponding reference compound, without red shift of the charge transfer band.     

Nonlinear optical properties of novel H-shaped chromophores

Novel and effective H-shaped chromophores were doped into polymethyl methacrylate (PMMA) to form guest-host polymer thin films.The measurement results of Maker fringe method show that the polymer thin films containing the H-shaped chromophores as a guest exhibit high second harmonic coefficients (d33) compared with other two-dimensional chromophores.     

含苯并噻唑氟化聚酰亚胺制备及非线性光学性质

采用Mitsunobu反应将杂环偶氮生色分子键入氟化聚酰亚胺母体制备新型的侧链含氟聚酰亚胺非线性光学(NLO)材料.采用傅里叶变换红外(FT-IR)光谱、紫外-可见(UV-Vis)光谱、1H核磁共振(1HNMR)谱和凝胶色谱(GPC)对材料进行表征.热分析结果表明侧链型聚酰亚胺具有较高的玻璃化转变温度(Tg)(184-188℃),热分解温度(Td)高达322℃.采用简单全反射法于1550nm处测定聚酰亚胺的电光系数(γ33),含苯并噻唑偶氮苯胺的聚酰亚胺(PI1)具有较高的电光系数15pm·V-1.