铂(II)氮杂环亚丙二烯基配合物的合成，磷光性质和自组装

PLATINUM(II) N HETEROCYCLIC ALLENYLIDENE COMPLEXES: SYNTHESIS, PHOSPHORESCENCE AND SELF ASSEMBLY

高琴

11649062

硕士

化学

陆为

2018

2018.7.11

哈尔滨工业大学

深圳

磷光金属芳香炔、卡宾和异腈配合物的研究在材料科学和光化学领域产生巨大的影响，其在有机发光二极管，超分子自组装，化学传感器和光催化等方面表现出良好的应用前景。将这个研究方向继续拓展，具有长寿命激发态的累积烯烃与过渡金属的配合物将会开辟新一代的功能性金属配合物。我们将着眼于氮杂环亚丙二烯基金属配合物的研究，这类配体与氮杂环卡宾相似和相应芳香异腈配体互为等电子体关系。氮杂环亚丙二烯基中线性的亚丙二烯基不仅可以增强M-Cα键，而且可以作为电子传输的导电线。基于此，本课题选用d8电子构型的铂(II)金属中心，成功合成并表征了6个中性内盐型和8个离子型铂(II)金属氮杂环亚丙二烯基化合物，所有配合物通过1H NMR、13C NMR、19F NMR、31P NMR、HR-MS、IR等进行结构确证和表征，并且得到10个单晶结构。室温时这些化合物固体发560-1000 nm的磷光，在稀溶液中也有磷光发射，其磷光寿命在几百纳秒左右。一些化合物还表现出有趣的超分子自组装性质。其中2-吡啶氮杂环亚丙二烯基内盐型化合物基于其两亲性结构，在DMSO或DMF与水的混合溶剂中形成亚稳态溶液，该溶液从动力学亚稳态到热力学平衡态的转化过程表现出有趣的自组装过程。通过调节溶剂极性，化合物浓度和温度等外部因素，从而调节Pt…Pt、π-π和氢键等弱相互作用力，最终形成发光不同的聚集体，不同聚集体之间还可以发生相互转变。对于离子型铂配合物，通过晶体结构表征，论文中阐述了这类化合物Pt…Pt距离不同对固体磷光性质的影响，一些离子型铂(II)氮杂环亚丙二烯基化合物，由于d8电子构型的平面四边形配位的特征，在Pt…Pt和π-π作用的驱动下，可以克服静电排斥力和位阻作用，组装形成Pt…Pt一维金属无限长链，产生3MMLCT辐射跃迁，在近红外区980 nm左右有磷光发射。

Luminescent metal-carbon complexes containing acetylide, N-heterocyclic carbine (NHC) and isocyanide ligands are well documented to have enormous impact to the development of materials science and photochemistry, and their applications in OLEDs, supramolecular self-assembly, chemosensors, and photocatalysts have high-performance. Along this line of research, N-heterocyclic allenylidene (NHA) was chosen as a new class of functional ligands, which is similar with NHC ligand of σ-donation from α-carbon and is also isoelectronic with isocyanide. The linear allenylidene bridge not only strengthens the M-Cα bond, but also can be a conductive wire for charge transport.In this thesis, platinum(II) with d8 electron configuration was choosen as metal center, and we synthesized a series of platinum(II) N-heterocyclic allenylidene complexes, including 6 zwitterionic and 8 ionic complexes. Basic characterizations including 1H NMR, 13C NMR, 19F NMR, 31P NMR, HR-MS and IR were carried out and we obtained 10 new single crystals characterized by single X-ray diffraction. All of them showed phosphorescence in solid and in fluid at room temperature, and the emission maximum of solid ranged from 560 nm to 1000 nm with lifetime about hundreds nanoseconds scale. Some of them had intriguing self-assembly properties. For a zwitterionic complex, based on its amphipathy, it could be dissolved in the mixture of DMSO or DMF and H2O and a kinetic solution was obtained, which inhibited kinetic and thermodynamics controlling self-assembly process. When adjusting the solvent polarity, temperature and concentration, there were different competitive pathways, finally different aggregates with diffrernt phosphorescence emerged. Besides, for ionic complexes, the relationship between phosphorescence and Pt…Pt interaction was revealed and some Pt(II) ionic complexes formed intriguing infinite Pt…Pt long chains characterized by single X-ray diffraction, which is driven by Pt…Pt and π-π interaction. And some complexes emit phophosrescence in near infrared region (ca.980 nm) in solid, which is attributed to 3MMLCT.

氮杂环亚丙二烯基 3MMLCT 自组装 近红外磷光

N-heterocyclic allenylidene 3MMLCT self-assembly NIR emission

中文

联合培养

南方科技大学

高琴. 铂(II)氮杂环亚丙二烯基配合物的合成，磷光性质和自组装[D]. 深圳. 哈尔滨工业大学,2018.