Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.     

Novel photoswitching dithienylethenes with ferrocene units

Two novel dithienylethenes with ferrocene units were synthesized by Wittig reaction. The structure of 2a has been established by X‐ray diffraction studies. They could reversibly interconvert between two thermally stable forms, an open and a closed one, using light of different wavelengths as triggers. Copyright © 2006 John Wiley & Sons, Ltd.     

Novel Properties of Photochromic Spirooxazine Nanoparticles

The nanoparticles of a spirooxazine （SPO） and its photomerocyanine （PMC） were prepared through the reprecipitation method. Two distinct features were observed. One is that the decaying lifetime for PMC nanoparticles was 600 times of that for the dispersed molecules, and the other is that the fluorescence intensity of SPO nanoparticles was enhanced by 240 times of that of the dispersed monomer.     

多钼酸盐–柠檬酸复合膜的多色光致变色

制备了多钼酸盐–柠檬酸光致变色复合膜，紫外光照后发现不同摩尔比的复合膜呈现不同的颜色。当摩尔比为1.0，0.3和0.2时，变色后的薄膜分别显深蓝色，深黄褐色和淡海绿色。通过对薄膜的拉曼光谱分析证实呈现不同的颜色是由于在变色后的膜中生成了不同的物种。柠檬酸在光致变色过程中起着重要的作用, 在紫外光的照射下它作为空穴的捕获剂, 抑制了光生电子和空穴的复合, 使多钼酸盐呈现紫外光致变色现象。     

N，N＇－1，4－亚丁基双〔螺吲哚啉萘并噁嗪〕的合成

在无水乙醇中，１－亚硝基－２萘酚同Ｎ，Ｎ＇－１，４－亚丁基双［２，３，３－三甲基－３Ｈ－吲哚］溴化物反应制得Ｎ，Ｎ＇－亚丁基双［螺吲哚啉萘并嗪］，经ＩＲ，ＵＶ，￣１ＨＮＭＲ和元素分析确认了结构，并对其光致变色性能进行了初步的考察。     

Reversible Full‐Range Color Control of a Cholesteric Liquid‐Crystalline Film by using a Molecular Motor

By using a chiral molecular motor as a dopant in a cholesteric liquid‐crystalline film, fully reversible control of the reflection color of this film across the entire visible spectrum is possible. The large difference in helical twisting power between the two isomeric forms of the motor allows efficient light‐ and heat‐induced switching of the helicity of the cholesteric liquid‐crystal superstructure.     

Synthesis and photochromic properties of 4-[2-(anthracen-9-yl)-5-methyloxazolyl] fulgide

New photochromic fulgide, viz., 4-{1-[2-(anthracen-9-yl)-5-methyloxazol-4-yl]ethylidene}-3-isopropylidenetetrahydrofuran-2,5-dione, with fluorescent properties was synthesized. Studies by electronic, IR, and ¹H NMR spectroscopy and X-ray diffraction demonstrated that this fulgide exists in the Z form. Light irradiation of its solutions at a wavelength of 365 nm causes Z/E isomerization giving rise to the thermally stable cyclic form. The latter is transformed into the starting E isomer under light irradiation at λ = 436 nm. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 97–101, January, 2006.     

Dialing in color with rare earth metals: facile photoluminescent production of true white light

Combining polymeric architectures with metal ions produces hybrid materials with extremely rich properties. We are studying polymers containing terpyridine in the side chain. In this report, the chelation of lanthanide ions, Eu³⁺, Tb³⁺, and Dy³⁺ resulted in metal functionalized copolymers that exhibited excellent emission of red, green, and blue light respectively. The polymer architecture easily allows incorporation of all three colors into the material, which leads to the facile production of true white light in solution or the solid state. Quantum efficiencies for the polymer systems were determined. The white light system had an efficiency of 5%. Various combinations of colors were achieved from the basic RBG colors by simply varying the metal ion ratios in the polymer backbone. This easy tuning of the color makes these systems attractive. Copyright © 2007 John Wiley & Sons, Ltd.     

含苯氧基萘并萘醌和偶氮苯双变色基化合物的合成和性质

通过６－氯－５，１２－萘并萘醌与４－羟基偶氮苯及其衍生物的反应合成了３种含苯氧基萘并萘醌和偶氮苯光致变色基的双变色基化合物，６－［４－（苯偶氮基）苯氧基］－５，１２－萘并萘醌（５），６－［４－（ｐ－乙氧基苯偶氮基）苯氧基］－５，１２－萘并萘醌（６）和６－［４－（ｐ－硝基苯偶氮基）苯氧基］－５，１２－萘并萘醌（７）．这些化合物的苯氧基萘并萘醌变色基的ＵＶ诱导光致变色性较弱；基于氨与苯氧基萘并萘醌ａｎａ显色体的不可逆反应，化合物５和６ＤＭＳＯ溶液在３６５ｎｍ紫外光辐照光稳态（ＰＳＳ）下的ａｎａ醌式摩尔分数估计分别为２２％和１７％．这些结果说明，苯偶氮基对苯氧基萘并萘醌变色基的光致变色性质有着极强的影响．另一方面，与４－羟基偶氮苯母体不同，这些双变色基化合物在ＤＭＳＯ中偶氮苯变色基的顺式异构体是相对稳定的     

静电自组装聚电解质/有机染料插层蒙脱土光致变色纳米复合膜

从构筑静电自组装聚电解质／有机染料插层蒙脱土光致变色纳米复合膜所必需 的基本纳米构件--有机染料插层蒙脱土光致变色纳米复合物的设计出发，制备了具有光致 变色功能的蒙脱土／阳离子偶氮染料（GTL）均插层纳米复合物现，插人蒙脱土层 间的GTL热稳定性大幅度提高．由于GTL在纳米受限空间的超分子有序结构共轭，使 偶氮基发生了高达91 nm的显著红移．使用该插层纳米复合物构件与阳离子聚电解 质（PDAC）通过静电自组装得到了生长均匀、排列规整有序的光致变色聚电解质／ 阳离子偶氮染料插层蒙脱土纳米复合膜.