多支结构的均三嗪衍生物的合成及双光子吸收性质

合成了3个系列各含有单支、双支和三支结构的9个均三嗪衍生物, 测定了它们的线性吸收和发射性质以及双光子吸收和发射性质. 随着三嗪环上侧链数目的增加, 线性吸收谱(吸收峰位于390～440 nm)、荧光谱(发射峰位于460～580 nm)和双光子荧光谱(激发波长800 nm)都发生红移; 各种光谱的强度逐渐增强; 基态与激发态的偶极矩之差Δμ_eg也逐渐增大. 另外, 从单支到三支结构, 双光子吸收截面σ随侧链数目呈非线性增加. 这表明多支结构的双光子吸收存在显著的增强效应.     

双光子吸收聚合引发剂EPVPVC的合成和非线性光学性质的研究

合成了一个新的双光子吸收聚合引发剂,9-乙基-3-{2-[4-(2-吡啶基-4-乙烯基)-苯基]-乙烯基}-9氢咔唑 (EPVPVC),用¹H NMR谱、¹³C NMR谱和元素分析进行了表征.测试了紫外吸收光谱、单光子荧光光谱、单光子荧光寿命、单光子荧光量子产率和双光子荧光光谱.量化计算结果表明,EPVPVC的双光子吸收截面为56.6×10^-50 cm⁴·s·photon^-1.在780 nm的飞秒脉冲激光激发下,EPVPVC发出较强的上转换荧光,荧光峰位于536 nm.用EPVPVC做引发剂,加入丙烯酸酯型齐聚物(cN120C80),在脉冲宽度为200 fs,重复频率为76 MHz,中心波长为780 nm 飞秒脉冲激光下,制作了一个三维周期性微结构.在理论计算的基础上,定性地探讨了其可能的聚合机理.     

分枝结构对以N为耦合中心的多分枝分子的双光子吸收性质的影响

采用ZINDO/SOS方法,研究了以N原子为耦合中心,以二苯乙烯类、噻吩类和芴类分子作为分枝的分子的双光子吸收性质,从而研究了分枝结构对多分枝分子的双光子吸收性质的影响.结果表明分枝结构会影响分枝之间耦合作用的强弱,因而对分子的双光子吸收性质具有重要影响.所设计的分子中以二苯乙烯类和噻吩类分子作为分枝的多分枝分子具有较大的双光子吸收截面.     

新型双光子吸收化合物的合成、光物理及其在固态分散体系中的性质

通过多步反应制备了三个新型的双光子吸收化合物,测试了它们的光物理性质,发现该系列化合物具有较大的双光子吸收截面,并且随温度降低其双光子吸收截面增大.尤其是化合物TMVDB,其量子效率为0.83,常温时的双光子吸收截面达到1164GM,其双光子吸收截面除以分子量为2.08,表现出了优良的双光子吸收发光性能.进一步将TMVDB掺杂到固体材料中,得到强双光子诱导发光的固体材料.     

多支型长链均三嗪衍生物的合成与光谱性质

合成了三个较长共轭链的均三嗪类衍生物, 分别为单支的L1、双支的L2、三支的L3, 并与相应的三个较短共轭链的均三嗪类衍生物(S1, S2, S3)做了比较. 实验结果表明, 在弱极性溶剂中, 随着三嗪环上侧链数目的增加或侧链的加长, 吸收光谱和荧光光谱的峰位(λ_max)都发生红移, 吸收强度和荧光强度都显著增强.     

卟啉多枝分子合成与分子内能量转移、双光子吸收性能研究

以三苯胺或硝基苯为端基, 合成了三个卟啉多枝分子: 5-(4-硝基苯甲酰氧基)苯基-10,15,20-三-(4-溴苯基)卟啉(TPP-NO₂)、5-(4-硝基苯甲酰氧基)苯基-10,15,20-三-(4-二苯胺基-1-苯乙烯基)苯基卟啉(TPP-X₃)和5,10,15,20-四-(4-二苯胺基-1-苯乙烯基)苯基卟啉(TPP-X₄), 进行了红外光谱、核磁共振光谱和质谱表征. 比较研究了分子“枝”、“核”不同键合方式与不同对称结构对分子的线性光谱、非线性光谱以及分子内能量转移行为的影响. 在钛宝石激光器(800 nm)和Nd∶YAG倍频光(532 nm)泵浦下, 样品溶液均发出卟啉环特有的红色荧光——前者系双光子吸收机制“上转换”荧光, 后者则为双光子吸收与分子内能量转移机制“下转换”荧光. 飞秒Z-scan技术测得样品双光子吸收截面最大可达130 GM, 与四苯基卟啉(TPP)同等测试条件下的双光子吸收截面相比增大了两个数量级.     

两个新型双光子吸收化合物的合成、结构和非线性光学性质

成功合成了两个具有双光子吸收性质的三苯胺衍生物：三-[4-（4-三氟甲基-1,3-丁二酮）苯基]胺（1）三-[4-（4-苯基-1,3-丁二酮）苯基]胺（2）,并使用元素分析,红外,核磁和质谱进行了表征.通过单晶X-射线衍射分析,发现分子具有D-（π-A）3的结构.同时研究了化合物在多种溶剂中的单,双光子吸收和荧光性质.基于双光子吸收原理的光学数据存储实验证明化合物在数据存储方面有潜在的应用价值.     

三芳基咪唑类化合物的合成及其双光子吸收性能研究

双光子吸收是指物质分子或原子在强激光激发下同时吸收两个光子,从基态跃迁到两倍光子能量激发态的过程。目前,双光子吸收材料已广泛地应用到双光子激发显微[1]、频率上转换激射[2-3]、光学限幅、三维光信息存储[4]以及光生物学等领域。但在已报道的双光子诱导上转换荧光的有机     

苯并噻唑衍物的合成及结构-双光子吸收光物理特性关系

报道了三个具有典型A-π-A'型共轭结构的苯并噻唑衍生物的合成及结构-双光 子吸收光物理特性关系。通过对三个化合物的共轭结构增长和拉电子基强度变化对 化合物单光子荧光光谱、双光子诱导荧光光谱和双光子吸收截面等特性的影响研究 ，我们发现，苯并噻唑杂环中的杂原子硫在化合物共轭链链短时对其光物理特性影 响很强，在共轭链较长时影响减弱甚至消失。通常情况下，共轭链长度和拉电子基 强度共同对双光子吸收截面作贡献，我们的研究表明，当共轭链较长时，共轭链的 增长对增强分子双光子吸收截面的贡献远大于拉电子基强度变化的贡献。其中，新 化合物2（2-{4-[2-（4-硝基苯基）-乙烯基]苯基}-乙烯基）苯并噻唑具有双光子 吸收截面大(181*10~(-50)cm~4s/photon)和荧光量子产率高(13.8%)的特点，是双 光子荧光显微与成像应用的一个良好的候选材料。     

苯并噻唑衍物的合成及结构-双光子吸收光物理特性关系

报道了三个具有典型A-π-A'型共轭结构的苯并噻唑衍生物的合成及结构-双光 子吸收光物理特性关系。通过对三个化合物的共轭结构增长和拉电子基强度变化对 化合物单光子荧光光谱、双光子诱导荧光光谱和双光子吸收截面等特性的影响研究 ，我们发现，苯并噻唑杂环中的杂原子硫在化合物共轭链链短时对其光物理特性影 响很强，在共轭链较长时影响减弱甚至消失。通常情况下，共轭链长度和拉电子基 强度共同对双光子吸收截面作贡献，我们的研究表明，当共轭链较长时，共轭链的 增长对增强分子双光子吸收截面的贡献远大于拉电子基强度变化的贡献。其中，新 化合物2（2-{4-[2-（4-硝基苯基）-乙烯基]苯基}-乙烯基）苯并噻唑具有双光子 吸收截面大(181*10~(-50)cm~4s/photon)和荧光量子产率高(13.8%)的特点，是双 光子荧光显微与成像应用的一个良好的候选材料。     

Synthesis and Two-photon Absorption Properties of s-Triazine Derivatives

Two new s-triazine derivatives, which belong to linear dipolar type and triangle octupolar type respectively, have been synthesized. The structure of the dipolar compound has been determined by X-ray diffraction. The two-photon absorption cross-section σ, and the two-photon excited fluorescence (TPEF) intensities are increased significantly from dipolar compound to octupolar compound.     

Anthrathiadiazole Derivatives: Synthesis,Physical Properties and Two-photon Absorption

Anthrathiadiazole is a key synthon for the construction of large azaacenes, however, the attachment of different substituents onto the skeleton of anthrathiadiazole is difficult but highly desirable because it could be easy to enrich the structures of azaacenes. Here, it is demonstrated that anthrathiadiazole derivatives with −Br, −CN, and −OCH₃ groups could be easily constructed through a simple [4+2] cycloaddition reaction between a,a,a’,a’-tetrabromo-o-xylenes derivatives and benzo[c][1,2,5]thiadiazole-4,7-dione. The structures of the as-prepared compounds with different substituents were carefully characterized. Moreover, the basic physical properties of the as-prepared anthrathiadiazole derivatives were fully investigated, where the cyano-substituted derivative (BTH - CN) has the highest stability and the methoxy-substituted derivative ( BTH - OCH₃) is easy to be oxidized. Moreover, the two-photon absorption (TPA) characteristics of different anthrathiadiazoles are also studied by using the femtosecond Z-scan technique. The results show that the fused anthrathiadiazole skeletons possess large TPA cross-section values δ₂ in the range of 3000–5000 GM, where the nature, position and strength of the substituted groups have strong effect on these values.     

有机双光子吸收材料研究进展

有机双光子吸收材料是光电信息功能材料领域的研究热点之一.同无机双光子吸收材料相比,有机双光子吸收材料有更好的可设计性和可裁接性.从分子设计的角度介绍了国内外所取得的一些最新进展,并对有机双光子吸收材料的发展方向作了综述.     

Theoretical Studies on the Third-order Nonlinear Optical Properties and Two-photon Absorption of Stilbene Derivatives

Different types of stilbene derivatives (D-π-D, A-π-A, D-π-A) were investigated with AM1, and specially, equilibrium geometries of symmetrical stilbene derivatives (D-π-D) were studied using of PM3. With the same method INDO/CI, the UV-vis spectra were explored and the position and strength of the two-photon absorption were predicated by Sum-Over-States expression. The relationships of the structures, spectra and nonlinear optical properties have been examined. The influence of various substituents on two photon absorption cross-sections was discussed micromechanically.     

Synthesis, Structure of a Symmetrically Substituted Stilbene with Strong Two-photon Absorption and Up-converted Blue Fluorescence

Symmetric substituted stilbenes have significantly potential application such as fluorescence microscopy, two-photon photodynamic therapy, optical power limiting, and three-dimensional storage1-2. These dyes have strong tendency of symmetric intra-molecular change transfer under the excited state. As a result, they usually exhibit large two-photon absorptivity (TPA), in the meanwhile emit strong up-converted fluorescence. On the other hand, their solutions generally display linear transmis…     

New Thiophene Derivatives with Two-photon Excited Fluorescence

Organic molecules that can simultaneously absorb two or more photons in reaching theirexcited states have recently been the subject in various photon-electronic fields. Tomeet the criteria for various nonlinear optical applications, such as three-dimensionaloptical storage1 and up-converted lasing2, molecules with large two-photon absorption(TPA) cross-section σ are required and have been synthesized. These dyes generallybelong to the structural modes of D-π-D, A-π-A3 or D-π-A, where D…