Planar π-extended cycloparaphenylenes featuring an all-armchair edge topology

Xiang, Feifei; Maisel, Sven; Beniwal, Sumit; Akhmetov, Vladimir; Ruppenstein, Cordula; Devarajulu, Mirunalini; Dörr, Andreas; Papaianina, Olena; Görling, Andreas; Amsharov, Konstantin; Maier, Sabine

doi:10.1038/s41557-022-00968-3

Cited by 26 publications

(22 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These results are especially relevant in the context of recent endeavours toward synthesis of combined linear and kinked systems, especially the circulenes and planar cycloparaphenylenes that have been recently synthesized. [23][24][25] Since the linear and kinked PAHs have starkly different behavior in their ST gaps as well as stability, tunable ST gapped systems that are stable can be predicted based on the observations in our work. 36 K. Fujise, E. Tsurumaki, K. Wakamatsu and S. Toyota, Chemistry-A European Journal, 2021, 27, 4548-4552.…”

Section: Discussionmentioning

confidence: 61%

“…17,18 While the electronic properties of polyacenes have long been studied and understood, 2,[11][12][13] relatively little is known about the electronic structure of helicenes and phenacenes. [19][20][21][22] This is even more crucial in the context of the recent synthesis of planar and non-planar structures of circulenes 23,24 and phenylenes 25 , which are a combination of linear and non-linear arrangements of benzene rings.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The Curious Case of Low-lying States in Non-linear Pol- yaromatic Hydrocarbons

Dey

Ghosh

2022

Preprint

View full text Add to dashboard Cite

The prediction of accurate singlet triplet (ST) gaps of polyaromatic hydrocarbons has been challenging due to the differential multireference character of the two states. The ST gaps of linear polyacenes have shown an exponential decay with system size due to the decreasing stability and increasing multireference nature of the singlet state. These low ST gaps can ideally be leveraged towards energy applications but is hindered by the decreasing stability of the system. While non-linear or kinked polyacenes are characterised by higher stability, multireference calculations on these systems are limited. In our work, we show that while the singlet states of kinked polyacenes are markedly less multireference, the triplet states are highly multireference in these systems and therefore, the correct trend of ST gap in the kinked polyacenes requires high-level multireference calculations. We show that unlike linear polyacenes, in the non-linear systems the ST gaps increase marginally with system size. The ST gaps also show absolutely no correlation with HOMO-LUMO gaps. These surprising trends are a combined effect of the non-linear connections (topology) and the geometrical factors. These results are in stark contrast to the observations in linear polyacenes.

show abstract

Section: Discussionmentioning

confidence: 61%

Section: Introductionmentioning

confidence: 99%

The Curious Case of Low-lying States in Non-linear Pol- yaromatic Hydrocarbons

Dey

Ghosh

2022

Preprint

View full text Add to dashboard Cite

show abstract

“…[n]cycloparaphenylenes ([n]CPPs)-closed rings of phenylenes linked in the para position-possess desirable πelectron delocalization along the carbon backbone, but the high strain in these systems prevents their π-extension into either larger or planar structures. Now, a collaboration led by Sabine Maier and Andreas Görling at Friedrich-Alexander-Universität Erlangen-Nürnberg and Konstantin Amsharov at Martin-Luther-Universität Halle-Wittenberg in Germany describes the on-surface synthesis of planar π-extended [12]CPP, featuring an all-armchair edge topology, whereby the peripheral phenylene units are solely para-conjugated (https://doi.org/10.1038/s41557-022-00968-3) 1 .…”

Section: Research Highlightmentioning

confidence: 99%

On-surface synthesis of planar π-extended [12]cycloparaphenylene

Richards

2022

Commun Chem

View full text Add to dashboard Cite

show abstract

“…[2] During the past years, a large number of structurally welldefined NGs with various sizes and topological features have been synthesized in solution and on metal surfaces. [3] Triangulenes, a unique class of zigzag-edged triangular NGs, have attracted long-standing interest owing to their openshell ground states and intriguing magnetic properties. [4] However, their high reactivity towards oxygen makes solution synthesis extremely challenging, [5] and hence, recent advances in the synthesis of unsubstituted [n]triangulenes (n represents the number of carbon atoms across the zigzag edge) exclusively utilize on-surface chemistry under ultrahigh vacuum (UHV) conditions.…”

mentioning

confidence: 99%

Heteroatom‐Edged [4]Triangulene: Facile Synthesis and Two‐Dimensional On‐Surface Self‐Assemblies**

Chen

et al. 2022

Angewandte Chemie

View full text Add to dashboard Cite

Triangulenes have attracted enormous interest in organic chemistry and materials science, but suffer from their high instability towards oxygen. Embedding heteroatoms into triangulenes provides a new class of ambient stable materials for various applications. However, [3]heterotriangulenes have dominated the chemistry of heteroatom‐doped triangulenes, while their higher homologues have been rarely explored. In this work, we synthesize a new [4]heterotriangulene with three oxygen‐boron‐oxygen (OBO) segments incorporated into the zigzag edges. The planar geometry of the OBO‐doped [4]triangulene is demonstrated by single‐crystal X‐ray diffraction. Self‐assembly on metal surfaces reveals substrate‐dependent nanostructures, leading to different long‐range ordered 2D patterns on Ag and Cu substrates with negligible defects.

show abstract

Planar π-extended cycloparaphenylenes featuring an all-armchair edge topology

Cited by 26 publications

References 54 publications

The Curious Case of Low-lying States in Non-linear Pol- yaromatic Hydrocarbons

The Curious Case of Low-lying States in Non-linear Pol- yaromatic Hydrocarbons

On-surface synthesis of planar π-extended [12]cycloparaphenylene

Heteroatom‐Edged [4]Triangulene: Facile Synthesis and Two‐Dimensional On‐Surface Self‐Assemblies**

Contact Info

Product

Resources

About