Synthesis of Giant Dendritic Polyphenylenes with 366 and 546 Carbon Atoms and Their High-vacuum Electrospray Deposition

Overview

Journal Chem Asian J

Specialty Chemistry

Date 2022 Apr 5

PMID 35381624

Authors

Ian Cheng-Yi Hou

Antoine Hinaut

Sebastian Scherb

Ernst Meyer

Akimitsu Narita

Klaus Mullen

Affiliations

Soon will be listed here.

Abstract

Dendritic polyphenylenes (PPs) can serve as precursors of nanographenes (NGs) if their structures represent 2D projections without overlapping benzene rings. Here, we report the synthesis of two giant dendritic PPs fulfilling this criteria with 366 and 546 carbon atoms by applying a "layer-by-layer" extension strategy. Although our initial attempts on their cyclodehydrogenation toward the corresponding NGs in solution were unsuccessful, we achieved their deposition on metal substrates under ultrahigh vacuum through the electrospray technique. Scanning probe microscopy imaging provides valuable information on the possible thermally induced partial planarization of such giant dendritic PPs on a metal surface.

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Synthesis of Giant Dendritic Polyphenylenes with 366 and 546 Carbon Atoms and Their High-vacuum Electrospray Deposition.

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References

Rempala P, Kroulik J, King B . Investigation of the mechanism of the intramolecular Scholl reaction of contiguous phenylbenzenes. J Org Chem. 2006; 71(14):5067-81. DOI: 10.1021/jo0526744. View

Giovannantonio M, Yao X, Eimre K, Urgel J, Ruffieux P, Pignedoli C . Large-Cavity Coronoids with Different Inner and Outer Edge Structures. J Am Chem Soc. 2020; 142(28):12046-12050. PMC: 7467669. DOI: 10.1021/jacs.0c05268. View

Zhao W, Huang L, Guan Y, Wulff W . Three-component asymmetric catalytic Ugi reaction--concinnity from diversity by substrate-mediated catalyst assembly. Angew Chem Int Ed Engl. 2014; 53(13):3436-41. PMC: 4010135. DOI: 10.1002/anie.201310491. View

Wagner J, Li L, Simon J, Krutzke L, Landfester K, Mailander V . Amphiphilic Polyphenylene Dendron Conjugates for Surface Remodeling of Adenovirus 5. Angew Chem Int Ed Engl. 2020; 59(14):5712-5720. PMC: 7155148. DOI: 10.1002/anie.201913708. View

Rogers C, Chen C, Pedramrazi Z, Omrani A, Tsai H, Jung H . Closing the Nanographene Gap: Surface-Assisted Synthesis of Peripentacene from 6,6'-Bipentacene Precursors. Angew Chem Int Ed Engl. 2015; 54(50):15143-6. DOI: 10.1002/anie.201507104. View

Hammer B, Mullen K . Expanding the limits of synthetic macromolecular chemistry through Polyphenylene Dendrimers. J Nanopart Res. 2018; 20(10):262. PMC: 6182379. DOI: 10.1007/s11051-018-4364-6. View

Feng X, Wu J, Enkelmann V, Mullen K . Hexa-peri-hexabenzocoronenes by efficient oxidative cyclodehydrogenation: the role of the oligophenylene precursors. Org Lett. 2006; 8(6):1145-8. DOI: 10.1021/ol053043z. View

Hu Y, Xie P, De Corato M, Ruini A, Zhao S, Meggendorfer F . Bandgap Engineering of Graphene Nanoribbons by Control over Structural Distortion. J Am Chem Soc. 2018; 140(25):7803-7809. DOI: 10.1021/jacs.8b02209. View

Bai J, Duan X, Huang Y . Rational fabrication of graphene nanoribbons using a nanowire etch mask. Nano Lett. 2009; 9(5):2083-7. DOI: 10.1021/nl900531n. View

10.

Hammer B, Moritz R, Stangenberg R, Baumgarten M, Mullen K . The polar side of polyphenylene dendrimers. Chem Soc Rev. 2014; 44(12):4072-90. DOI: 10.1039/c4cs00245h. View

11.

Hinaut A, Meier T, Pawlak R, Feund S, Johr R, Kawai S . Electrospray deposition of structurally complex molecules revealed by atomic force microscopy. Nanoscale. 2018; 10(3):1337-1344. DOI: 10.1039/c7nr06261c. View

12.

Tan Y, Yang B, Parvez K, Narita A, Osella S, Beljonne D . Atomically precise edge chlorination of nanographenes and its application in graphene nanoribbons. Nat Commun. 2013; 4:2646. PMC: 3831289. DOI: 10.1038/ncomms3646. View

13.

Wu J, Pisula W, Mullen K . Graphenes as potential material for electronics. Chem Rev. 2007; 107(3):718-47. DOI: 10.1021/cr068010r. View

14.

Zhu Y, Guo X, Li Y, Wang J . Fusing of Seven HBCs toward a Green Nanographene Propeller. J Am Chem Soc. 2019; 141(13):5511-5517. DOI: 10.1021/jacs.9b01266. View

15.

Kawasumi K, Zhang Q, Segawa Y, Scott L, Itami K . A grossly warped nanographene and the consequences of multiple odd-membered-ring defects. Nat Chem. 2013; 5(9):739-44. DOI: 10.1038/nchem.1704. View

16.

Nguyen T, Baumgarten M, Rouhanipour A, Rader H, Lieberwirth I, Mullen K . Extending the limits of precision polymer synthesis: giant polyphenylene dendrimers in the megadalton mass range approaching structural perfection. J Am Chem Soc. 2013; 135(11):4183-6. DOI: 10.1021/ja311430r. View

17.

Saywell A, Sprafke J, Esdaile L, Britton A, Rienzo A, Anderson H . Conformation and packing of porphyrin polymer chains deposited using electrospray on a gold surface. Angew Chem Int Ed Engl. 2010; 49(48):9136-9. DOI: 10.1002/anie.201004896. View

18.

Hinaut A, Pawlak R, Meyer E, Glatzel T . Electrospray deposition of organic molecules on bulk insulator surfaces. Beilstein J Nanotechnol. 2015; 6:1927-34. PMC: 4660929. DOI: 10.3762/bjnano.6.195. View

19.

Simpson C, Mattersteig G, Martin K, Gherghel L, Bauer R, Rader H . Nanosized molecular propellers by cyclodehydrogenation of polyphenylene dendrimers. J Am Chem Soc. 2004; 126(10):3139-47. DOI: 10.1021/ja036732j. View

20.

Hammer B, Mullen K . Dimensional Evolution of Polyphenylenes: Expanding in All Directions. Chem Rev. 2015; 116(4):2103-40. DOI: 10.1021/acs.chemrev.5b00515. View