基于含氟吡咯并吡咯二酮（DPP）电子化学品的合成及其电化学性能研究

1,4-Diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole and its derivatives based π extended conjugated systems, so-called DPPs, exbibit excellent optoelectronic properties and has been applied to functional materials. The synthesis of fluorinated diphenyl-diketopyrrolopyrrole derivatives is difficult and rarely reported, and fluorinated DPPs have not been studied in electrochemical area, the application of electroplating engineering in particular. In conjunction with our continuing efforts for researching on the synthesis of DPPs and their applications in fluorescence probe, fluorescence material and so on, a series of fluoro-DPPs are to be designed and synthesized, and it is necessary to expand the methodology of synthesis of fluoro-DPPs to obtain more derivatives. Moreover, it discovered that the structure-electrochemical behavior relationships of DPPs containing fluorocarbon groups to suggest that it has been identified as highly promising electric materials for future electroplated engineering processing. This project will focus on: Firstly, DPPs are modified with different fluorocarbon groups on their aromatic rings by fluoro-reactions such as fluoro-alkylation and fluorination reaction, and fluoroalkyl side chains and fluorine-containing aromatic compounds can be introduced into the N-positions of the DPP unit; and fluoro-DPPs are generated directly from succinate and aromatic nitriles. Secondly, in order to obtain water-soluble DPPs, water-soluble units were introduced into DPP derivatives to improve their water solubility and their interfacial properties were studied. Then, we study how the molecular structures of fluorinated DPPs effect the properties of their photo-spectra and electrochemistry, and the effects of supramolecular π-π stacking and “fluorine-effect” and its application mechanism in electroplating engineering were studied.

吡咯并吡咯二酮（DPP）具有独特的共轭体系而显示出优良的光电性能被广泛应用于功能材料中。然而含氟DPP衍生物合成条件苛刻却鲜有报道，且其电化学性能研究和在电镀工程学上的应用尚属空白。该申请基于本课题组前期研究DPP衍生物合成方法以及其荧光性能的基础上，设计和合成系列含氟DPP衍生物且构建合成含氟DPP的方法学，继而研究含氟DPP的结构和其电化学性能之间的关系，探索其作为电子化学品在电镀工程中的应用机理。首先，使用不同的含氟试剂和DPP分子中的芳环进行反应，如进行单氟以及氟烷基取代反应；其次，在DPP分子中杂环氮原子上以含氟链以及含氟芳基衍生物的进行反应修饰，亦以含氟芳香腈合成系列含氟DPP衍生物；再次，在DPP分子中引入水溶性单元来提高其水溶性并研究其界面性能，接着研究含氟DPP分子结构对其光谱、电化学等性质的影响，研究其超分子π-π堆积效应和“氟效应”以及其在电镀工程中的应用机制。

吡咯并吡咯二酮(DPP)是一种高性能的有机颜料，其具有共平面结构和较强的分子内氢键和π-π 堆积效应，因此其显示出优良的光电性能被广泛应用于功能材料中。.首先，使用不同的含氟试剂和DPP分子中的芳环进行反应，进行单氟以及氟烷基取代反应；其次，在DPP分子中杂环氮原子上以含氟链以及含氟芳基衍生物的进行反应修饰，亦以含氟芳香腈合成系列含氟DPP衍生物, 通过电化学和镀铜测试，结果表明含氟DPP季铵盐其整平效果远高于其他DPP季铵盐；进而基于吡咯并吡咯二酮结构合成了一系列不同杂环取代的DPP季铵盐，通过测试表明含硒的五元杂环DPP季铵盐具有较好的整平效果。其后，将双吡啶鎓(Bipyridinium)作为亲水基团接枝到吡咯并吡咯二酮(DPP)的两端，得到吡咯并吡咯二酮衍生物，再将其与并与葫芦7脲(CB [7])组装在一起，制备了超分子化合物，通过对其电化学进行测试，研究了组装前后分子的抑制性能及其与其他添加剂的协同作用，结果显示其具有优秀的抑制能力，且可以与PEG-10000和SPS发挥协同作用，从而获得优异的盲孔填充效果。随后通过DFT计算与MD模拟对超分子化合物在电镀中的作用机理进行了研究，实际的盲孔填充电镀测试结果表明，添加2 μmol/L的该助剂后能够导致自下而上的填充均匀，达到理想的镀铜效果，填充效率(η)为97.7％，这表明了通过主客体作用能改变DPP整平剂的整平性能。总之，本项目合成了系列含氟DPP季铵盐整平剂，研究了电镀机理和电镀工艺，用于PCB电路板电镀中与商品化整平剂JGB的电镀抑制性能对比，结果表明DPP季铵盐拥有更强的抑制能力，因此可作为潜在的PCB电路板电镀整平剂，是具有应用推广前景的湿电子化学品。