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中文摘要：
由于超分子体系在生物体系和生命过程中重要的功能作用，有机纳米结构的制备、结构、功能性质的研究已经成为化学和材料科学中的热点研究领域之一。本课题的主要目标是设计合成具有特异结构和性质（例如光学，电学或者磁学功能性质）的卟啉、酞菁类金属配位化合物，利用共轭分子间强烈的pi-pi相互作用协同氢键、配位键、静电相互作用等多重分子间弱相互作用来调节和控制聚集体的形貌和结构，发展新的纳米聚集态的构筑方法,制备高阶有序的有机纳米聚集体结构并用于OFET、非线性光学材料、分子开关等的研究。同时对共轭大环配合物高级有序纳米聚集体的构筑、结构与性能关系开展理论和实验两方面的研究，探索分子结构－纳米结构－器件性能的关系。寻求进一步设计合成具有更高性能的新型功能材料和器件的思路和方法。
英文摘要：
porphyrin；phthalocyanine；self assembly；organic aggregate；OFET
结论摘要：
计划研究内容集中于对卟啉、酞菁类金属配位化合物进行分子设计、合成，对其有序高级结构分子聚集体的构筑、结构与性能关系开展理论和实验两方面的研究。设计合成具有特异结构和性质的卟啉、酞菁类化合物及其金属配合物，用于非线性光学材料及分子电子器件等功能性质研究。对该类分子材料的有序聚集体、有机纳米结构的制备、电子器件的加工和性质进行系统研究，并通过杂化和掺杂对材料的性能进行调控。探索利用新的物理化学现象设计分子电子器件和聚集体分子材料电子器件的方法，研究分子结构－纳米结构－器件性能的关系。自2010年1月项目启动以来，按照研究计划开展工作，取得了重要进展，完成了预定研究目标。取得成果包括1、设计制备了一系列新颖的卟啉酞菁类化合物及其过渡金属和稀土金属配合物，特别是利用新的合成方法首次制备了卟啉酞菁的四层、五层和六层混杂稀土-过渡金属配合物与新型席夫碱-酞菁混杂稀土-过渡金属配合物，并通过稀土磁性离子的引入，获得了一系列新型稀土单分子磁体，研究了它们的构效关系以及分子内磁性离子间相互作用等问题，为进一步调控和优化三明治型稀土配合物的单分子磁体等功能性质提供了新的方向。2、以功能为导向实现了不同类型的有机半导体分子材料的结构设计与性能调控。通过在酞菁环周边引入烷氧基作为供电子基团，引入羧基、烷基、磺酰基或对氟苯氧基等作为吸电子基团，用以调控有机半导体材料的本征性能，获得了电子迁移率占主导地位的n-型半导体分子材料、空穴迁移率占主导地位的p-型半导体分子材料和空穴/电子迁移率平衡的双极性半导体分子材料。3、通过理性的分子设计、组装条件的调控，有效的调控了分子间的相互作用，获得了不同形貌的纳米自组装结构，实现了聚集体结构的可控制备，揭示了分子结构以及分子间作用力与聚集形貌之间的联系，特别是，发现了pH值控制的有机纳米晶体与大块单晶之间的可逆转换现象，应该是第一例有机纳米晶体与单晶的可逆转化，从而提供一种有效的合成晶态材料的新方法，为有机纳米材料的进一步研究与应用提供了支持。项目执行期间应邀出版专著1部，撰写专著章节1章，发表SCI收录论文80余篇，其中影响因子5.0以上论文22篇。应邀在国际会议上做邀请报告7次，国内会议上做大会和邀请报告7次，培养博士研究生23名（毕业13名）、硕士研究生22名（毕业12名）、培养在站博士后7名（在站3名）。
成果综合统计
期刊论文
会议论文
专利
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著作
期刊论文
Nature of the Near-IR Band in the Electronic Absorption Spectra of Neutral Bis(tetrapyrrole) Rare Ea
Optically Active Homoleptic Bis(phthalocyaninato) Rare Earth Double-Decker Complexes Bearing Periphe
Toward panchromatic organic functional molecules: Density functional theory study on the nature of t
Controlling the directionality of charge transfer in phthalocyaninato zinc sensitizer for a dye-sens
Structures and properties of novel 5,15-di[4-(5-acetylsulfanylpentyloxy)phenyl] porphyrin derivative
Morphology Controlled Surface-Assisted Self-Assembled Microtube Junctions and Dendrites of Metal Fre
Synthesis, crystal structure and self-assembly property of a mixed (phthalocyaninato) (porphyrinato)
Helical Nanostructures of an Optically Active Metal-Free Porphyrin with Four Optically Active Binaph
Diverse Ni(II) MOFs constructed from asymmetric semi-rigid V-shaped multicarboxylate ligands: struct
Benzo-fused low symmetry metal-free tetraazaporphyrin and phthalocyanine analogs: synthesis, spectro
Linkage Dependence of Intramolecular Fluorescence Quenching Process in Porphyrin-Appended Mixed (Pht
Structures and Spectroscopic Properties of Fluoroboron-Subtriazaporphyrin Derivatives: Density Funct
Synthesis, characterization and cytotoxic activity of 5,10,15,20-tetrakis[4-(triorganostannyloxy)phe
Self-assembled nanostructures of optically active phthalocyanine derivatives. Effect of central meta
Interfacial assembly of sandwich mixed (Phthalocyaninato)(Porphyrinato) rare earth triple-decker com
Sandwich-type tetrakis(phthalocyaninato) rare earth(III)-cadmium(II) quadruple-deckers. The effect o
Synthesis, crystal structure and magnetic properties of a new 2D cyanide-bridged heterobimetallic Cr
Organic field effect transistors based on 5,10,15,20-tetrakis(4-pentyloxyphenyl)porphyrin single cry
Heterobimetallic porphyrin-based single-chain magnet constructed from manganese(III)-porphyrin and t
Nanoscale Hollow Spheres of an Amphiphilic Mixed (Phthalocyaninato)(porphyrinato)europium Double-Dec
Mixed (phthalocyaninato)(porphyrinato) heterometal complexes with sandwich quadruple-decker molecula
Nature of the Intense Near-IR Absorption and Unusual Broad UV-Visible-NIR Spectra of Azulenocyanines
Novel Pathway to Synthesize Unsymmetrical 2,3,9,10,16,17,23-heptakis(alkoxyl)24-mono(dimethylaminoal
Periphery-Hydrogenating Effects on the Unordinary 14 p-Electron Delocalized Circuits and Related Ele
Optically Active Mixed (Phthalocyaninato)(Porphyrinato) Rare Earth Triple-Decker Complexes. Synthesi
Conformational effects, molecular orbitals, and reaction activities of bis(phthalocyaninato) lanthan
Twist angle perturbation on mixed (phthalocyaninato)(porphyrinato) dysprosium(III) double-decker SMM
Synthesis, Crystal Structures, and Magnetic Properties of One-Dimensional Mixed Cyanide- and Phenola
Tetrakis(phthalocyaninato) Rare-Earth-Cadmium-Rare-Earth Quadruple-Decker Sandwich SMMs: Suppression
Bis[1,4,8,11,15,18,22,25-octa(butyloxyl)phthalocyaninato] rare earth double-decker complexes: synthe
Fusing Phthalocyanine and Porphyrin together: Unprecedented Co-planar Ring-Fused Diazaphthalocyanina
Helical nano-structures self-assembled from dimethylaminoethyloxy-containing unsymmetrical octakis-s
Mixed (porphyrinato)(phthalocyaninato) rare-earth(III) double-decker complexes for broadband light h
Morphology and chirality controlled self-assembled nanostructures of porphyrin-pentapeptide conjugat
Ferrocene-Decorated (Phthalocyaninato)(Porphyrinato) Double- and Triple-Decker Rare Earth Complexes:
Sandwich-type mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes with decreas
The first solution-processable n-type phthalocyaninato copper semiconductor: tuning the semiconducti
A Special Conjugated Model around sp3 Carbon Atoms: Density Functional Theory Study on the Homoaroma
Organic Nanostructures with Controllable Morphology Fabricated from Mixed (Phthalocyaninato)(porphyr
Facile approaches to build ordered amphiphilic tris(phthalocyaninato) europium triple-decker complex
Synthesis, Electrochemical and Spectroscopic Properties of C(60)-Porphyrin Dyads with Different Phen
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