Roth Alexandra, Schaub Tobias A, Meinhardt Ute, Thiel Dominik, Storch Jan, Církva Vladimír, Jakubík Pavel, Guldi Dirk M, Kivala Milan
Institute for Physical Chemistry I , Department Chemistry and Pharmacy , University of Erlangen-Nürnberg , Egerlandstrasse 3 , D-91058 Erlangen , Germany . Email:
Institute for Organic Chemistry I , Department of Chemistry and Pharmacy , University of Erlangen-Nürnberg , Henkestrasse 42 , D-91054 Erlangen , Germany . Email:
Chem Sci. 2017 May 1;8(5):3494-3499. doi: 10.1039/c7sc00533d. Epub 2017 Feb 24.
,'-Didodecyl-substituted 3,10-diazapicenium salts featuring bromide and hexafluorophosphate counterions have been designed as novel dopants to realize individualized graphene sheets in a series of cutting edge experiments and to intrinsically stabilize them p-doping. Importantly, electrochemical studies revealed two consecutive irreversible one-electron reductions of the ,'-didodecyl-substituted 3,10-diazapicenium salts to yield the corresponding radical cation and neutral quinoidal species. Formation of both species was accompanied by characteristic changes in the absorption spectra. The 3,10-diazapicenium bromide was found to be a potent dopant to produce hybrid materials with exfoliated graphene. Microscopy based on AFM and TEM imaging and spectroscopy based on Raman probing corroborated that, upon drying, the hybrid material consists of few layer (5-8 layers) turbostratic graphene sheets that are p-doped. Our findings identify the newly synthesized ,'-dialkylated 3,10-diazapicenium salts as highly promising candidates for the fabrication of functional graphene materials with tailored properties.
具有溴化物和六氟磷酸盐抗衡离子的 1,1'-二癸基取代的 3,10-二氮杂芘盐已被设计为新型掺杂剂，用于在一系列前沿实验中实现个性化石墨烯片并从本质上稳定它们的 p 型掺杂。重要的是，电化学研究表明，1,1'-二癸基取代的 3,10-二氮杂芘盐发生了连续两次不可逆的单电子还原，生成相应的自由基阳离子和中性醌类物质。这两种物质的形成都伴随着吸收光谱的特征变化。发现 3,10-二氮杂芘溴化物是一种有效的掺杂剂，可用于制备具有剥离石墨烯的混合材料。基于原子力显微镜（AFM）和透射电子显微镜（TEM）成像的显微镜技术以及基于拉曼探测的光谱技术证实，干燥后，混合材料由几层（5-8 层）层错石墨烯片组成，这些石墨烯片被 p 型掺杂。我们的研究结果表明，新合成的 1,1'-二烷基化 3,10-二氮杂芘盐是制备具有定制性能的功能石墨烯材料的极具潜力的候选材料。
