不对称方酸菁的合成、性质和应用

综述了不对称方酸菁的合成、中间体的制备、光谱、光导性能以及应用研究。     

近红外水溶性不对称吲哚方酸菁染料的合成

以吲哚啉季铵盐为原料, 分别采用两步法和固相法合成了3种水溶性不对称吲哚方酸菁染料. 两步法为将不同N-烷基取代的2,3,3-三甲基-3H-吲哚-5-磺酸季铵盐与方酸反应, 再与另一种吲哚啉季铵盐反应制备不对称菁染料. 固相法是用对氨基苯甲酸做桥连物, 将方酸化学键连到高分子固相载体聚乙二醇上, 然后与吲哚啉季铵盐杂环母核缩合制得带有固相高分子载体的半菁, 再与另一吲哚啉季铵盐杂环母核反应切掉载体, 合成不对称菁染料. 产品用C-18反相柱进行分离提纯, 通过核磁共振氢谱和质谱对产品结构进行了表征, 测试了产品的光谱性能. 比较而言, 固相法合成不对称染料效果更好, 产率接近传统两步法的二倍, 是一种更适合的合成水溶性不对称吲哚方酸菁染料的方法.     

新型水溶性荧光标示剂吲哚方酸菁染料的合成及光谱性能

用方酸与不同的N烷基取代吲哚啉季铵盐缩合制备了一系列对称的水溶性方酸菁染料. 通过核磁共振氢谱和质谱对合成的染料结构进行了表征, 研究了它们在不同溶剂中的吸收和发射光谱. 结果表明, 随着溶剂极性的增大, 染料的吸收光谱发生蓝移, 表现为负向溶剂化效应, 在极性溶剂中的荧光量子产率比在水中的大. 考察了N位取代基对染料水溶液光稳定性的影响, 结果表明在吲哚环N原子上引入较大的苄基有助于提高光稳定性, 且随着苄基上取代基吸电子能力的增强, 染料的光稳定性增强.     

冠醚方酸碲碳菁染料的合成研究

合成了不对称冠醚方酸碲碳菁染料和对称冠醚方酸碲碳菁染料，并探讨了对称冠醚方酸碲碳菁的合成方法及反应条件，提出了其可能的反应机理。     

含碲唑杂环的不对称碳菁及方酸菁的合成与性质

以苯并碲唑季铵碘盐为原料，将其与３－乙基－２－（β－乙酰苯胺）乙烯工噻唑磺化季铵盐在无水吡啶中回流，得到４个含碲不对称碳菁染料，上述季铵盐与方酸的反应不 般杂环碱，只能发生１：１缩合反应，缩合产物与苯并噻唑碘盐在正丁醇／吡啶中反应即得含碲不对称方酸菁染料，该法避免了通常制备不对称方酸菁所带来的分离纯化的困难，从而提供了制备不对称方酸碲菁染料的通用方法，研究了不对称碲碳菁的“Ｂｒｏｏｋｅｒ偏差”，结     

新型多臂方酸菁化合物的合成及光谱性质

合成了引入多甘醇醚链的５－Ｎ，Ｎ－双（２－羟乙基）胺基－１，３－间苯二酚及其衍生物，使之与方酸发生缩合反应，获得了７种新型多臂方酸菁化合物，研究了它们的光谱性质     

方酸菁染料掺杂聚对苯乙炔太阳电池研究

本文把方酸菁染料掺杂在聚[2-甲氧基-5(2-乙基己氧基)对苯乙炔](MEH-PPV)共轭聚合物中,利用方酸菁染料在可见光的良好吸收以提高器件对光谱的利用。用Ti(OC3H7)4作为纳米TiO2前驱物直接和MEH-PPV、方酸菁染料(Hydroxy Squaraine,Sq)混合旋涂来制作连续的互穿网络器件。通过紫外-可见光吸收光谱得到掺杂后体系在650nm左右吸收得到加强,通过荧光测试发现体系MEH-PPV(5mg/mL)∶Sq(0.1mg/1mL)为4∶1(v∶v)掺杂Ti(OC3H7)4(80μL/mL)体积为50%时,荧光几乎被完全淬灭。测试了器件ITO/MEH-PPV/∶Sq∶TiO2/A,ITO/TiO2/MEH-PPV∶Squaraine∶TiO2/A l的光电性能,在AM=1.5,1000W/m2白光下单层器件的FF为0.31,Voc=54Mv,Isc=1.4mA,能量转换效率为0.008%。在同样条件下双层器件FF为0.12,Voc=203mV,Isc=0.048mA,能量转换效率为0.009%。     

方酸菁染料在有机太阳能电池中的研究进展

方酸菁作为一种重要的菁类染料,由于它在可见-近红外区有强烈的吸收和发射性质,以及良好的光热稳定性,使它在太阳能电池的研究中越来越受到重视.随着理论的不断完善,以及太阳能电池制作技术的成熟,方酸菁将在这一领域继续得到快速发展.综述了近年来方酸菁染料在染料敏化太阳能电池和本体异质结太阳能电池中的应用,从机理角度着重讨论了染料分子结构等因素对电池性能的影响,并提出了未来的研究方向.     

含N-烷基吲哚环方酸菁染料的合成及性能

本文合成了七个N-烷基取代吲哚环的方酸菁染料,通过红外光谱、核磁共振氢谱、质谱与元素分析确认其结构。测定它们的电子吸收光谱、熔点、溶解度和光褪色。结果表明共轭链上引入方酸桥环提高了光稳定性,N-烷基对染料的λmax的影响很小,但较大地改进了溶解度与熔点,带有支链的烷基有更好的溶解性能。     

方酸菁荧光探针的应用研究进展

功能性方酸菁染料具有独特的D-A-D共轭结构,其在可见光和近红外区域有强烈的吸收和荧光发射。方酸菁染料作为近红外荧光探针母体被应用于蛋白质、氨基酸、一些生物小分子、环境污染物及金属离子等的检测。本文结合课题组近几年工作综述了方酸菁染料在蛋白质、氨基酸、生物小分子、阳离子和其它物质检测方面的应用。     

不对称双二茂铁脲衍生物的合成、表征及电子传递性质

以二茂铁为原料,通过多步反应,首先合成了对称的桥联双二茂铁脲(5),再将其与胱胺反应,合成了一种新的不对称桥 联双二茂铁脲衍生物MeOOC-Fc-NH-CO-NH-Fc-CO-NH-(CH₂)₂-S-S-(CH₂)₂-NH₂ (7)(Fc：二茂铁)。对目标产物进行了红外、紫外、¹H NMR和MS表征;由于目标化合物7含有不对称的二茂铁脲这一特殊结构,采用循环伏安(CV)方法对化合物7的电子迁移特性进行了研究。结果表明2个二茂铁之间通过脲键传递电子,从而使2个二茂铁基团可以分别被氧化,它们的氧化电位差ΔE_o^?为181 mV,它们之间的稳定常数Kc为1 145。相对于对称的二茂铁脲(5)(ΔE_o^?=140 mV,K_c=207),这种不对称结构分子中2个二茂铁之间电子间的相互作用增强。     

不对称方酸染料的电子结构与光导性的从头算研究

用量子化学从头算法,在RHF/6-31G(d,p)水平上优化了八种不对称方酸染料的分子构型,并对它们的分子内电荷转移程度与暗衰值,光敏值和最大吸收波长的定量关系进行研究,发现不对称方酸染料的分子内电荷转移性质,是影响不对称方酸染料光导性和最大吸收波长的重要因素。     

含苯并五元环方酸衍生物的二阶非线性光学性质的理论研究

利用从头算HF/6-31G*方法对用苯并五元环取代的方酸衍生物体系SQ1～SQ15进行几何构型优化和电子结构计算. 以优化后的构型为基础, 应用ZINDO方法计算电子光谱. 同时应用从头算CPHF/6-31G*方法和半经验FF/AM1, FF/PM3, FF/MNDO等有限场方法计算了分子的二阶非线性光学系数β_μ. 研究几何结构、电子结构和前线分子轨道能与β_μ之间的关系, 为设计性能优良的有机非线性光学材料提供理论指导, 并对这四种计算方法的结果进行了比较.     

Synthesis and Molecular Properties of Acceptor‐Substituted Squaraine Dyes

A broad series of more than 20 acceptor‐substituted squaraines was synthesized that feature different acceptor functionalities at the central squaraine four‐membered ring. The influence of these acceptor units on the reactivity of semisquaraine precursors and stability of the respective squaraines were explored. Thereby the dicyanovinyl group was found to be the most versatile acceptor group that enabled various modifications at the donor moiety of the squaraine scaffold, leading to an extended series of dicyanovinyl‐functionalized squaraines. The variation of donor units afforded a set of NIR fluorophores that cover a wavelength region from the visible at about 650 nm far into the NIR up to 920 nm with fluorescence quantum yields between 0.93 and 0.11 and outstanding optical brightness. This excellent optical property is related to a rigid molecular scaffold that is fixed in an all‐cis configuration by the additional dicyanovinyl acceptor unit. The change of the molecular symmetry from C_2h to C_2v upon functionalization of the squaraine core with dicyanovinyl acceptor group has been confirmed in solution by electro‐optical absorption (EOA) spectroscopy, revealing permanent ground‐state dipole moments μ_g in the range between 4.3 and 6.4 D. These dipole moments direct an antiparallel packing of the molecules in the solid state according to single‐crystal X‐ray analyses achieved for four dicyanovinyl‐functionalized squaraines. The structural properties, the EOA results, as well as the band shapes of the optical spectra indicate that these polymethine dyes are cyanine‐type chromophores. It is worth noting that the orientation of the dipole moment vectors is orthogonal to the orientation of the transition dipole moment vectors, which is an uncommon but characteristic feature of this rather novel class of polymethine dyes. With regard to applications of these dyes in organic solar cells, their redox properties were also studied by cyclic voltammetry.     

Helicity Control in the Aggregation of Achiral Squaraine Dyes in Solution and Thin Films

Squaraine dyes are well known for their strong absorption in the visible regime. Reports on chiral squaraine dyes are, however, scarce. To address this gap, we here report two novel chiral squaraine dyes and their achiral counterparts. The presented dyes are aggregated in solution and in thin films. A detailed chiroptical study shows that thin films formed by co-assembling the chiral dye with its achiral counterpart exhibit exceptional photophysical properties. The circular dichroism (CD) of the co-assembled structures reaches a maximum when just 25 % of the chiral dye are present in the mixture. The solid structures with the highest relative CD effect are achieved when the chiral dye is used solely as a director, rather than the structural component. The chiroptical data are further supported by selected spin-filtering measurements using mc-AFM. These findings provide a promising platform for investigating the relationship between the dissymmetry of a supramolecular structure and emerging material properties rather than a comparison between a chiral molecular structure and an achiral counterpart.     

Synthesis and Spectroscopic Studies of Some Novel Quinoline Derivatives

An intramolecular Wittig reaction of some substituted aminoacetophenones was used for the synthesis of novel quinoline derivatives. In addition, the base induced cyclization of the aminoacetophenones was investigated. The IR and NMR spectra of the quinoline derivatives are reported.     

新型含双酚衍生物三枝氟硼二吡咯染料的合成及其光物理性能

以三聚氯氰为原料合成含醛基的二酚氧基取代中间体（1）; 1分别与酚衍生物（2a~2e）经取代反应制得三酚氧基中间体（3a~3e）; 3a~3e经缩合、氧化和配位等反应合成了5个新型的含双酚衍生物三枝氟硼二吡咯（BODIPY）荧光染料（4a~4e）,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。4a~4e的最大吸收波长和发射波长分别位于499 nm和508 nm,荧光量子产率为0.41~0.55,显示出BODIPY荧光核典型的光物理性能。