Multilayer Stacks of Polycyclic Aromatic Hydrocarbons

Overview

Journal Nat Chem

Specialty Chemistry

Date 2022 Feb 8

PMID 35132223

Authors

Magnus Mahl

M A Niyas

Kazutaka Shoyama

Frank Wurthner

Affiliations

Soon will be listed here.

Abstract

Polycyclic aromatic hydrocarbons (PAHs) show promise for applications in functional devices such as organic photovoltaics and field-effect transistors, but, although nanometre-sized PAHs-often referred to as nanographenes-have been well investigated as single-layer molecules, their multilayer counterparts remain rather unexplored. Here we show the assembly of a C nanographene derivative (comprising a planar core decorated with four meta-terphenyl-imide moieties at its periphery) into multilayer stacks with smaller PAHs ranging from naphthalene to ovalene and hexabenzocoronene. The functionalized C nanographene serves as a ditopic host that can accommodate a smaller PAH on either side of its planar core, in cavities delimited by its bulky imide substituents. Bilayers and trilayers (that is, complexes with 1:1 and 1:2 host:guest ratios, respectively) were observed in solution, and dimers of these complexes as well as multilayer compounds were isolated in the solid state. Quantum-chemical calculations indicate that dispersion forces are the main stabilizing factor for these complexes.

Citing Articles

Bilayer nanographene reveals halide permeation through a benzene hole.

Niyas M, Shoyama K, Grune M, Wurthner F Nature. 2025; 637(8047):854-859.

PMID: 39814896 PMC: 11754092. DOI: 10.1038/s41586-024-08299-8.

Reductive Aromatization of 5,7,12,14-Pentacenetetrone: Approach Towards Substituted Pentacenes?.

Kleykamp O, Sharikow E, Stoy A, Xie X, Lichtenberg C, Sundermeyer J Chemistry. 2024; 31(8):e202403929.

PMID: 39670957 PMC: 11803357. DOI: 10.1002/chem.202403929.

Dialkylated dibenzo[,]anthracenes for solution-processable organic thin-film transistors.

Yang T, Zhang L, Bao Y, Wei H RSC Adv. 2024; 14(49):36390-36397.

PMID: 39545167 PMC: 11561707. DOI: 10.1039/d4ra07439d.

π-extended pyrenes: from an antiaromatic buckybowl to doubly curved nanocarbons with gulf architectures.

Liu B, Jin Z, Liu X, Sun L, Yang C, Zhang L Chem Sci. 2024; .

PMID: 39328190 PMC: 11421037. DOI: 10.1039/d4sc03460k.

Bimolecular Sandwich Aggregates of Porphyrin Nanorings.

Gotfredsen H, Hergenhahn J, Duarte F, Claridge T, Anderson H J Am Chem Soc. 2024; 146(36):25232-25244.

PMID: 39186461 PMC: 11403599. DOI: 10.1021/jacs.4c09267.

References

Novoselov K, Geim A, Morozov S, Jiang D, Zhang Y, Dubonos S . Electric field effect in atomically thin carbon films. Science. 2004; 306(5696):666-9. DOI: 10.1126/science.1102896. View

Georgakilas V, Otyepka M, Bourlinos A, Chandra V, Kim N, Kemp K . Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem Rev. 2012; 112(11):6156-214. DOI: 10.1021/cr3000412. View

Watson M, Jackel F, Severin N, Rabe J, Mullen K . A hexa-peri-hexabenzocoronene cyclophane: an addition to the toolbox for molecular electronics. J Am Chem Soc. 2004; 126(5):1402-7. DOI: 10.1021/ja037520p. View

Zhao X, Hou H, Fan X, Wang Y, Liu Y, Tang C . Molecular bilayer graphene. Nat Commun. 2019; 10(1):3057. PMC: 6624274. DOI: 10.1038/s41467-019-11098-9. View

Moshniaha L, Zyla-Karwowska M, Chmielewski P, Lis T, Cybinska J, Gonka E . Aromatic Nanosandwich Obtained by σ-Dimerization of a Nanographenoid π-Radical. J Am Chem Soc. 2020; 142(7):3626-3635. PMC: 7467677. DOI: 10.1021/jacs.9b13942. View

Young R, Wasielewski M . Mixed Electronic States in Molecular Dimers: Connecting Singlet Fission, Excimer Formation, and Symmetry-Breaking Charge Transfer. Acc Chem Res. 2020; 53(9):1957-1968. DOI: 10.1021/acs.accounts.0c00397. View

Zhang Y, Tang T, Girit C, Hao Z, Martin M, Zettl A . Direct observation of a widely tunable bandgap in bilayer graphene. Nature. 2009; 459(7248):820-3. DOI: 10.1038/nature08105. View

Cao Y, Rodan-Legrain D, Rubies-Bigorda O, Park J, Watanabe K, Taniguchi T . Tunable correlated states and spin-polarized phases in twisted bilayer-bilayer graphene. Nature. 2020; 583(7815):215-220. DOI: 10.1038/s41586-020-2260-6. View

Juricek M, Strutt N, Barnes J, Butterfield A, Dale E, Baldridge K . Induced-fit catalysis of corannulene bowl-to-bowl inversion. Nat Chem. 2014; 6(3):222-8. DOI: 10.1038/nchem.1842. View

10.

Dale E, Vermeulen N, Juricek M, Barnes J, Young R, Wasielewski M . Supramolecular Explorations: Exhibiting the Extent of Extended Cationic Cyclophanes. Acc Chem Res. 2016; 49(2):262-73. DOI: 10.1021/acs.accounts.5b00495. View

11.

Narita A, Wang X, Feng X, Mullen K . New advances in nanographene chemistry. Chem Soc Rev. 2015; 44(18):6616-43. DOI: 10.1039/c5cs00183h. View

12.

Stepien M, Gonka E, Zyla M, Sprutta N . Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds: Synthetic Routes, Properties, and Applications. Chem Rev. 2016; 117(4):3479-3716. DOI: 10.1021/acs.chemrev.6b00076. View

13.

Ito H, Segawa Y, Murakami K, Itami K . Polycyclic Arene Synthesis by Annulative π-Extension. J Am Chem Soc. 2018; 141(1):3-10. DOI: 10.1021/jacs.8b09232. View

14.

Hirai M, Tanaka N, Sakai M, Yamaguchi S . Structurally Constrained Boron-, Nitrogen-, Silicon-, and Phosphorus-Centered Polycyclic π-Conjugated Systems. Chem Rev. 2019; 119(14):8291-8331. DOI: 10.1021/acs.chemrev.8b00637. View

15.

Liang N, Meng D, Wang Z . Giant Rylene Imide-Based Electron Acceptors for Organic Photovoltaics. Acc Chem Res. 2021; 54(4):961-975. DOI: 10.1021/acs.accounts.0c00677. View

16.

Shoyama K, Mahl M, Seifert S, Wurthner F . A General Synthetic Route to Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed Annulation Reaction. J Org Chem. 2018; 83(10):5339-5346. DOI: 10.1021/acs.joc.8b00301. View

17.

Thordarson P . Determining association constants from titration experiments in supramolecular chemistry. Chem Soc Rev. 2010; 40(3):1305-23. DOI: 10.1039/c0cs00062k. View

18.

Dale E, Vermeulen N, Thomas A, Barnes J, Juricek M, Blackburn A . ExCage. J Am Chem Soc. 2014; 136(30):10669-82. DOI: 10.1021/ja5041557. View

19.

Horn P, Mao Y, Head-Gordon M . Probing non-covalent interactions with a second generation energy decomposition analysis using absolutely localized molecular orbitals. Phys Chem Chem Phys. 2016; 18(33):23067-79. DOI: 10.1039/c6cp03784d. View

20.

Cai J, Ruffieux P, Jaafar R, Bieri M, Braun T, Blankenburg S . Atomically precise bottom-up fabrication of graphene nanoribbons. Nature. 2010; 466(7305):470-3. DOI: 10.1038/nature09211. View