Triangulene

Last updated
Triangulene
Triangulene.svg
Names
Preferred IUPAC name
Dibenzo[cd,mn]pyrene-4,8-diyl
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/C22H12/c1-4-13-10-15-6-2-8-17-12-18-9-3-7-16-11-14(5-1)19(13)22(20(15)17)21(16)18/h1-12H
    Key: YUXIWEBPPQSVAK-UHFFFAOYSA-N
  • c1cc2cc3cccc4c3c-5c2c(c1)[CH]c6c5c(ccc6)[CH]4
Properties
C22H12
Molar mass 276.338 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Triangulene (also known as Clar's hydrocarbon) is the smallest triplet-ground-state polybenzenoid. [1] It exists as a biradical with the chemical formula C
22
H
12
. [2] It was first hypothesized by Czech chemist Erich Clar in 1953. [3] Its first confirmed synthesis was published in a February 2017 issue of Nature Nanotechnology, in a project led by researchers David Fox and Anish Mistry at the University of Warwick in collaboration with IBM. [4] Other attempts by Japanese researchers have been successful only in making substituted triangulene derivatives. [5]

Contents

A six-step synthesis yielded two isomers of dihydrotriangulene which were then deposited on xenon or copper base. The researchers used a combined scanning tunneling and atomic force microscope (STM/AFM) to remove individual hydrogen atoms. The synthesized molecule of triangulene remained stable at high-vacuum low-temperature conditions for four days, giving the scientists plenty of time to characterize it (also using STM/AFM). [4]

[n]Triangulenes

Triangulene, as defined in the previous paragraph, is a member of a wider class of [n]triangulenes, where n = 1, 2, 3 etc. is the number of hexagons along an edge of the molecule. Thus, triangulene may also be referred to as [3]triangulene.

Theory

A tight-binding description of the molecular orbitals of [n]triangulenes predicts [6] that [n]triangulenes have (n-1) unpaired electrons, which are associated to (n-1) non-bonding states. When electron-electron interactions are included, theory predicts [6] [7] [8] that the ground state total spin quantum number S of [n]triangulenes is S = (n-1)/2. Thus, [3]triangulenes are predicted to have an S = 1 ground state. The intramolecular exchange interaction in triangulene, which determines the energy difference between the S = 1 ground state and the S = 0 excited state, is predicted to be the largest [9] among all polycyclic aromatic hydrocarbon (PAH) diradicals, due to maximum overlap of the wave function of the unpaired electrons.

The ground state spin of [n]triangulenes can be rationalized [6] in terms of a theorem [10] by Elliot H. Lieb, which relates, for a bipartite lattice, the ground state spin of the Hubbard model at half filling to the sublattice imbalance.

Experiments

So far, the ultra-high vacuum on-surface syntheses of [n]triangulenes with n = 3, [4] 4, [11] 5 [12] and 7 [13] (the hitherto largest triangulene homologue) have been reported. In addition, the on-surface synthesis of [3]triangulene dimers [14] has also been reported, where inelastic electron tunneling spectroscopy provides a direct evidence of a strong antiferromagnetic coupling between the triangulenes. In 2021, an international team of researchers reported the fabrication of [3]triangulene-based quantum spin chains on a gold surface, [15] where signatures of both spin fractionalization and Haldane gap were observed.

Related Research Articles

Plasmon

In physics, a plasmon is a quantum of plasma oscillation. Just as light consists of photons, the plasma oscillation consists of plasmons. The plasmon can be considered as a quasiparticle since it arises from the quantization of plasma oscillations, just like phonons are quantizations of mechanical vibrations. Thus, plasmons are collective oscillations of the free electron gas density. For example, at optical frequencies, plasmons can couple with a photon to create another quasiparticle called a plasmon polariton.

Graphene Hexagonal lattice made of carbon atoms

Graphene is an allotrope of carbon consisting of a single layer of atoms arranged in a two-dimensional honeycomb lattice nanostructure. The name is derived from "graphite" and the suffix -ene, reflecting the fact that the graphite allotrope of carbon contains numerous double bonds.

A non-Kekulé molecule is a conjugated hydrocarbon that cannot be assigned a classical Kekulé structure.

Graphene nanoribbon Carbon allotrope

Graphene nanoribbons are strips of graphene with width less than 100 nm. Graphene ribbons were introduced as a theoretical model by Mitsutaka Fujita and coauthors to examine the edge and nanoscale size effect in graphene.

Graphane Chemical compound

Graphane is a two-dimensional polymer of carbon and hydrogen with the formula unit (CH)n where n is large. Partial hydrogenation is then hydrogenated graphene.

Topological insulator State of matter with insulating bulk but conductive boundary

A topological insulator is a material that behaves as an insulator in its interior but whose surface contains conducting states, meaning that electrons can only move along the surface of the material. Topological insulators have non-trivial symmetry-protected topological order; however, having a conducting surface is not unique to topological insulators, since ordinary band insulators can also support conductive surface states. What is special about topological insulators is that their surface states are symmetry-protected Dirac fermions by particle number conservation and time-reversal symmetry. In two-dimensional (2D) systems, this ordering is analogous to a conventional electron gas subject to a strong external magnetic field causing electronic excitation gap in the sample bulk and metallic conduction at the boundaries or surfaces.

Rodney S. Ruoff

Rodney S. "Rod" Ruoff is an American physical chemist and nanoscience researcher. He is one of the world experts on carbon materials including carbon nanostructures such as fullerenes, nanotubes, graphene, diamond, and has had pioneering discoveries on such materials and others. Ruoff received his B.S. in Chemistry from the University of Texas at Austin (1981) and his Ph.D. in Chemical Physics at the University of Illinois-Urbana (1988). After a Fulbright Fellowship at the MPI fuer Stroemungsforschung in Goettingen, Germany (1989) and postdoctoral work at the IBM T. J. Watson Research Center (1990–91), Ruoff became a staff scientist in the Molecular Physics Laboratory at SRI International (1991-1996). He is currently UNIST Distinguished Professor at the Ulsan National Institute of Science and Technology (UNIST), and the director of the Center for Multidimensional Carbon Materials, an Institute for Basic Science Center located at UNIST.

The AKLT model is an extension of the one-dimensional quantum Heisenberg spin model. The proposal and exact solution of this model by Affleck, Lieb, Kennedy and Tasaki provided crucial insight into the physics of the spin-1 Heisenberg chain. It has also served as a useful example for such concepts as valence bond solid order, symmetry-protected topological order and matrix product state wavefunctions.

Spin engineering describes the control and manipulation of quantum spin systems to develop devices and materials. This includes the use of the spin degrees of freedom as a probe for spin based phenomena. Because of the basic importance of quantum spin for physical and chemical processes, spin engineering is relevant for a wide range of scientific and technological applications. Current examples range from Bose–Einstein condensation to spin-based data storage and reading in state-of-the-art hard disk drives, as well as from powerful analytical tools like nuclear magnetic resonance spectroscopy and electron paramagnetic resonance spectroscopy to the development of magnetic molecules as qubits and magnetic nanoparticles. In addition, spin engineering exploits the functionality of spin to design materials with novel properties as well as to provide a better understanding and advanced applications of conventional material systems. Many chemical reactions are devised to create bulk materials or single molecules with well defined spin properties, such as a single-molecule magnet. The aim of this article is to provide an outline of fields of research and development where the focus is on the properties and applications of quantum spin.

Bilayer graphene is a material consisting of two layers of graphene. One of the first reports of bilayer graphene was in the seminal 2004 Science paper by Geim and colleagues, in which they described devices "which contained just one, two, or three atomic layers"

Potential graphene applications include lightweight, thin, and flexible electric/photonics circuits, solar cells, and various medical, chemical and industrial processes enhanced or enabled by the use of new graphene materials.

Transition metal dichalcogenide monolayers

Transition metal dichalcogenide (TMD or TMDC) monolayers are atomically thin semiconductors of the type MX2, with M a transition metal atom (Mo, W, etc.) and X a chalcogen atom (S, Se, or Te). One layer of M atoms is sandwiched between two layers of X atoms. They are part of the large family of so-called 2D materials, named so to emphasize their extraordinary thinness. For example, a MoS2 monolayer is only 6.5 Å thick. The key feature of these materials is the interaction of large atoms in the 2D structure as compared with first-row transition metal dichalcogenides, e.g., WTe2 exhibits anomalous giant magnetoresistance and superconductivity.

In materials science, the term single-layer materials or 2D materials refers to crystalline solids consisting of a single layer of atoms. These materials are promising for some applications but remain the focus of research. Single-layer materials derived from single elements generally carry the -ene suffix in their names, e.g. graphene. Single-layer materials that are compounds of two or more elements have -ane or -ide suffixes. 2D materials can generally be categorized as either 2D allotropes of various elements or as compounds.

Germanene

Germanene is a material made up of a single layer of germanium atoms. The material is created in a process similar to that of silicene and graphene, in which high vacuum and high temperature are used to deposit a layer of germanium atoms on a substrate. High-quality thin films of germanene have revealed unusual two-dimensional structures with novel electronic properties suitable for semiconductor device applications and materials science research.

A rapidly increasing list of graphene production techniques have been developed to enable graphene's use in commercial applications.

Graphene is a 2D nanosheet with atomic thin thickness in terms of 0.34 nm. Due to the ultrathin thickness, graphene showed many properties that are quite different from their bulk graphite counterparts. The most prominent advantages are known to be their high electron mobility and high mechanical strengths. Thus, it exhibits potential for applications in optics and electronics especially for the development of wearable devices as flexible substrates. More importantly, the optical absorption rate of graphene is 2.3% in the visible and near-infrared region. This broadband absorption characteristic also attracted great attention of the research community to exploit the graphene-based photodetectors/modulators.

Electronic properties of graphene

Graphene is a semimetal whose conduction and valence bands meet at the Dirac points, which are six locations in momentum space, the vertices of its hexagonal Brillouin zone, divided into two non-equivalent sets of three points. The two sets are labeled K and K'. The sets give graphene a valley degeneracy of gv = 2. By contrast, for traditional semiconductors the primary point of interest is generally Γ, where momentum is zero. Four electronic properties separate it from other condensed matter systems.

Two dimensional hexagonal boron nitride is a material of comparable structure to graphene with potential applications in e.g. photonics., fuel cells and as a substrate for two-dimensional heterostructures. 2D h-BN is isostructural to graphene, but where graphene is conductive, 2D h-BN is a wide-gap insulator.

Klaus Müllen

Klaus Müllen is a German chemist working in the fields of polymer chemistry, supramolecular chemistry and nanotechnology. He is known for the synthesis and exploration of the properties of graphene-like nanostructures and their potential applications in organic electronics.

The FLEUR code is an open-source scientific software package for the simulation of material properties of crystalline solids, thin films, and surfaces. It implements Kohn-Sham density functional theory (DFT) in terms of the all-electron full-potential linearized augmented-plane-wave method. With this, it is a realization of one of the most precise DFT methodologies. The code has the common features of a modern DFT simulation package. In the past, major applications have been in the field of magnetism, spintronics, quantum materials, e.g. in ultrathin films, complex magnetism like in spin spirals or magnetic Skyrmion lattices, and in spin-orbit related physics, e.g. in graphene and topological insulators.

References

  1. IUPAC , Compendium of Chemical Terminology , 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006) " biradical ". doi : 10.1351/goldbook.B00671
  2. "triangulene | C22H12 | ChemSpider". www.chemspider.com. Retrieved 2017-02-19.
  3. Ball, Philip (February 2017). "Elusive triangulene created by moving atoms one at a time". Nature. 542 (7641): 284–285. Bibcode:2017Natur.542..284B. doi: 10.1038/nature.2017.21462 . PMID   28202993. S2CID   4398214.
  4. 1 2 3 Pavliček, Niko; Mistry, Anish; Majzik, Zsolt; Moll, Nikolaj; Meyer, Gerhard; Fox, David J.; Gross, Leo (April 2017). "Synthesis and characterization of triangulene" (PDF). Nature Nanotechnology. 12 (4): 308–311. Bibcode:2017NatNa..12..308P. doi:10.1038/nnano.2016.305. PMID   28192389.
  5. Morita, Yasushi; Suzuki, Shuichi; Sato, Kazunobu; Takui, Takeji (2011). "Synthetic organic spin chemistry for structurally well-defined open-shell graphene fragments". Nature Chemistry. 3 (3): 197–204. Bibcode:2011NatCh...3..197M. doi:10.1038/nchem.985. PMID   21336324.
  6. 1 2 3 Fernández-Rossier, J.; Palacios, J. J. (23 October 2007). "Magnetism in Graphene Nanoislands". Physical Review Letters. 99 (17): 177204. arXiv: 0707.2964 . Bibcode:2007PhRvL..99q7204F. doi:10.1103/PhysRevLett.99.177204. hdl: 10045/25254 . PMID   17995364. S2CID   9697828.
  7. Wang, Wei L.; Meng, Sheng; Kaxiras, Efthimios (1 January 2008). "Graphene NanoFlakes with Large Spin". Nano Letters. 8 (1): 241–245. Bibcode:2008NanoL...8..241W. doi:10.1021/nl072548a. PMID   18052302.
  8. Güçlü, A. D.; Potasz, P.; Voznyy, O.; Korkusinski, M.; Hawrylak, P. (10 December 2009). "Magnetism and Correlations in Fractionally Filled Degenerate Shells of Graphene Quantum Dots". Physical Review Letters. 103 (24): 246805. arXiv: 0907.5431 . Bibcode:2009PhRvL.103x6805G. doi:10.1103/PhysRevLett.103.246805. PMID   20366221. S2CID   18754119.
  9. Ortiz, Ricardo; Boto, Roberto A.; García-Martínez, Noel; Sancho-García, Juan C.; Melle-Franco, Manuel; Fernández-Rossier, Joaquı́n (11 September 2019). "Exchange Rules for Diradical π-Conjugated Hydrocarbons". Nano Letters. 19 (9): 5991–5997. arXiv: 1906.08544 . Bibcode:2019NanoL..19.5991O. doi:10.1021/acs.nanolett.9b01773. PMID   31365266. S2CID   195218794.
  10. Lieb, Elliott H. (6 March 1989). "Two theorems on the Hubbard model". Physical Review Letters. 62 (10): 1201–1204. Bibcode:1989PhRvL..62.1201L. doi:10.1103/PhysRevLett.62.1201. PMID   10039602.
  11. Mishra, Shantanu; Beyer, Doreen; Eimre, Kristjan; Liu, Junzhi; Berger, Reinhard; Gröning, Oliver; Pignedoli, Carlo A.; Müllen, Klaus; Fasel, Roman; Feng, Xinliang; Ruffieux, Pascal (10 July 2019). "Synthesis and Characterization of π-Extended Triangulene" (PDF). Journal of the American Chemical Society. 141 (27): 10621–10625. doi:10.1021/jacs.9b05319. PMID   31241927. S2CID   195696890.
  12. Su, Jie; Telychko, Mykola; Hu, Pan; Macam, Gennevieve; Mutombo, Pingo; Zhang, Hejian; Bao, Yang; Cheng, Fang; Huang, Zhi-Quan; Qiu, Zhizhan; Tan, Sherman J. R.; Lin, Hsin; Jelínek, Pavel; Chuang, Feng-Chuan; Wu, Jishan; Lu, Jiong (July 2019). "Atomically precise bottom-up synthesis of π-extended [5]triangulene". Science Advances. 5 (7): eaav7717. Bibcode:2019SciA....5.7717S. doi: 10.1126/sciadv.aav7717 . PMC   6660211 . PMID   31360763.
  13. Mishra, Shantanu; Xu, Kun; Eimre, Kristjan; Komber, Hartmut; Ma, Ji; Pignedoli, Carlo A.; Fasel, Roman; Feng, Xinliang; Ruffieux, Pascal (2021). "Synthesis and characterization of [7]triangulene". Nanoscale. 13 (3): 1624–1628. doi:10.1039/d0nr08181g. PMID   33443270. S2CID   231605335.
  14. Mishra, Shantanu; Beyer, Doreen; Eimre, Kristjan; Ortiz, Ricardo; Fernández‐Rossier, Joaquín; Berger, Reinhard; Gröning, Oliver; Pignedoli, Carlo A.; Fasel, Roman; Feng, Xinliang; Ruffieux, Pascal (13 July 2020). "Collective All‐Carbon Magnetism in Triangulene Dimers". Angewandte Chemie International Edition. 59 (29): 12041–12047. arXiv: 2003.00753 . doi:10.1002/anie.202002687. PMC   7383983 . PMID   32301570.
  15. Mishra, Shantanu; Catarina, Gonçalo; Wu, Fupeng; Ortiz, Ricardo; Jacob, David; Eimre, Kristjan; Ma, Ji; Pignedoli, Carlo A.; Feng, Xinliang; Ruffieux, Pascal; Fernández-Rossier, Joaquín; Fasel, Roman (13 October 2021). "Observation of fractional edge excitations in nanographene spin chains". Nature. 598 (7880): 287–292. arXiv: 2105.09102 . doi:10.1038/s41586-021-03842-3. PMID   34645998. S2CID   234777902.