【作者】 黄国庆；

【导师】 杜国同；

【作者基本信息】 吉林大学 ， 微电子学与固体电子学， 2013， 博士

【摘要】 1、我们首次利用提高温度的策略合成了一系列不对称的镍酞菁。与传统的合成不对称酞菁方法相比，我们仅从一种邻苯二甲腈出发，合成A3B-type酞菁和A4-type酞菁，极大地节约原材料的使用，且两种产物的分离比传统方法更容易。2、制备的镍酞菁，除了酞菁传统的B带和Q带吸收，更重要的是在近红外区1110-1240nm有一个比较宽的吸收带，研究结果表明：这主要是由于酞菁分子间氢键作用产生的电荷转移带。我们采用KBr压片方法，在He-Cd激光器激发下研究这些酞菁的光致发光特性，研究结果表明：它们分别在近红外区865和1650nm有两个发光带。近红外特性使得这些酞菁可以潜在的应用在太阳能电池材料，理论上可以把目前器件的光电转化率提高一倍，相关工作正在进行。3、我们采用简单的溶剂扩散方法，制备了这些酞菁的1D纳米材料。结果表明：这些镍酞菁在氯仿和甲醇溶液界面处自组装成六棱纳米管，这是关于金属酞菁六棱纳米管的首次报道。另外，结合纳米材料的XRD和吸收光谱，我们合理推测出六棱纳米管的形成过程，这为以后自组装材料的研究奠定了基础。4、我们合成了一种铜酞菁，利用上面的溶解扩散方法研究材料的自组装特性。结果表明：铜酞菁在氯仿和甲醇溶液界面处自组装成双螺旋纳米棒，这一独特的性质使得这类材料可以潜在的应用在分子识别方面。另外，这是关于酞菁自组装双螺旋纳米材料的首次报道。更多还原

【Abstract】 Since accidentally discovered by the Braun and Tchemiac in1907, phthalocyanines(Pcs) have been greatly developed from the early of dye materials to nowmultifunctional materials, and widely be used in photodynamic therapy, dyesensitization solar cells, photosynthesis, organic solar cells, light storage and organiclight-emitting diodes. Pcs, as “tomorrow material”, not only behave the characteristicsof organic materials (good flexibility, low price and easy processing, etc.), but alsohave many unique advantages, such as: high light and heat stability, the strongabsorption in visible light, various modifiers and supramolecular interactions.Recently, for example, Pcs with near infrared (NIR) absorption, have attractedmore and more attentions from Pc’s scientists. Research on NIR material andtechnology is motivated by curiosity in the fundamental study and practicalapplications in a number of important sectors such as energy, communication,bio-imaging, sensing, and advanced optoelectronics. However, Pcs with absorptionbeyond1.0μm is rarely reported. It is mainly due to the difficultly synthesis of nearinfrared material. There are commonly two methods to synthesize near infraredmaterials:1) the materials with a push-pull structure, but the yield of Pcs are generallylow in this way;2) π-π conjugated materials: the synthesized phthalocyanine isgenerally not stable and poor solubility by this method. Therefore, the development ofnew synthetic strategies to synthsize Pcs with NIR absorption are facing challengesfor phthalocyanine scientists.Hydrogen bonding interaction generally existing in biological enzymes and proteins,we here report a series of asymmetric Pcs, which have a benzyl oxygen and threephenoxy. These Pcs not only have the traditional B and Q absorption, but also have awide absorption band in1100-1200nm. This is mainly due to the strong hydrogenbond interactions in-between them, and lead to form a charge transfer band. The synthesized Pcs have been characterazition with1H NMR,13C NMR,1H-13C NMR,IR, HR-MS and UV/Vis/NIR, and confirm the structure of the compounds. These Pcswith NIR-absotption can be potentially application in organic solar cells, opticalstorage, photodynamic therapy, light catalysis, nonlinear optical and near infraredlight emitting. We also research the electrochemical of these Pcs. The result show thatthe energy gap of the Pcs are around1.10eV, which is rarely reported in the organicmaterials.Near infrared light emitting diodes have been applications in sensors and opticalcommunication. Rencently, the used materials in near infrared light emitting diode aremost trivalent rare earth ions (Er3+, Tm3+and Yb3+). However, because these rareearth complexes have the first resonant or more order resonance vibration (resultfrom-OH) and near infrared luminescent quenching, and the4f-4f transition in rareearth complexes is parity prohibition, which lead to low luminous efficiency. It isimportant to synthesize some near infrared luminescent materials, which do notcontain organic rare earth ions. We here prepared the asymmetric Pcs with nearinfrared absorption band in1110-1120nm. When these Pcs in KBr are excited, theyshowed strong NIR luminescence at840-860nm and1600-1650nm, respectively.glow of these features make phthalocyanine application near-infrared light. These Pcscan be potential application in near-infrared light.Since supramolecular chemistry as an independent discipline, the nanostructurematerials through self-assembling methods have more and more attentions byscientists, because lots of the functional building blocks existing in nature isassembled by small building blocks. Pcs, as one of the important building blocks inself-assembled materials, can be self-organization into many functional materials bynon covalent bond interaction, such as hydrogen bonding, π–π stacking, andmetal-ligand coordination. The self-organization abilities of functional chromophoreshave been widely exploited to generate supramolecular architectures with improvedphotophysical and (opto)electronic properties as a result of excitonic interactionsbetween the dyes. Recently, some special supramolecular structures based onphthalocyanine and other materials have been reported, such as:1) Nolte and co-workers reports on the formation of helical, micrometer-long f bers in achloroform solution of a Pc molecule peripherally substituted with four crown ethermoieties and eight chiral, long alkyl chains;2) Long, extremely well-organizednanorods are formed in aqueous solution of the amphiphilic ZnPc–C60salt. TEMimages showed that the nanotubules are composed of many other nanorod-likesubstructures. These1-D, Pc-based micelle-like structures display remarkablephotophysical properties as a result of their nanometric organization, namely, animpressive stabilization of the charge separated state (ZnPc–C60) lifetime.Our previous research work on designing and synthesizing metallo-Pcs and1Dtubular structure of Pcs, help us find and obtain these asymmetrical Pcs. ThroughH-bonding interaction, these asymmetrical Pcs are inclined to self-assemble intohelical nanorods and hexrod nanotubes in the interface of CHCl3and CH3OH. Ourresults provide further insights into the interaction in molecular dimer, and mean thatthese Pcs have potential application in magnets and supramolecular architectures.更多还原