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The Geometry and Electronic Topology of Higher-Order Charged Möbius Annulenes†

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Department of Chemistry and the Center for Computational Chemistry, University of Georgia, Athens, Georgia 30605, Department of Chemical Engineering, Stanford University, 381 North South Mall, Stanford, California 94305, and Department of Chemistry, Imperial College London, South Kensington Campus, Exhibition Road, London SW7 2AY, U.K.
†Part of the “Walter Thiel Festschrift”.
*To whom correspondence should be addressed. E-mail: [email protected], [email protected]
‡University of Georgia.
⊥Imperial College London.
§Current address: Forest Research Laboratories, 49 Mall Drive, Commack, NY, 11725.
∥Current address: Dept. of Chemistry, Duke University, Box 97, Durham, NC 27705.
¶Current address: Stanford University.
Cite this: J. Phys. Chem. A 2009, 113, 43, 11619–11629
Publication Date (Web):July 28, 2009
https://doi.org/10.1021/jp902176a
Copyright © 2009 American Chemical Society
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Abstract

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Higher-order aromatic charged Möbius-type annulenes have been Lkrealized computationally. These charged species are based on strips with more than one electronic half-twist, as defined by their linking numbers. The B3LYP/6-311+G(d,p) optimized structures and properties of annulene rings with such multiple half-twists (C12H122+, C12H122−, C14H14, C18H182+, C18H182−, C21H21+, C24H242−, C28H282+, and C28H282−) have the nearly equal C−C bond lengths, small dihedral angles around the circuits, stabilization energies, and nucleus-independent chemical shift values associated with aromaticity. The topology and nature of Möbius annulene systems are analyzed in terms of the torus curves defined by electron density functions (ρ(r)π, ELFπ) constructed using only the occupied π-MOs. The π-torus subdivides into a torus knot for annulenes defined by an odd linking number (Lk = 1, 3π) and a torus link for those with an even linking number (Lk = 2, 4π). The torus topology is shown to map onto single canonical π-MOs only for even values of Lk. Incomplete and misleading descriptions of the topology of π-electronic Möbius systems with an odd number of half twists result when only signed orbital diagrams are considered, as is often done for the iconic single half twist system.

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This article is cited by 29 publications.

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  2. Young Mo Sung, Juwon Oh, Won-Young Cha, Woojae Kim, Jong Min Lim, Min-Chul Yoon, and Dongho Kim . Control and Switching of Aromaticity in Various All-Aza-Expanded Porphyrins: Spectroscopic and Theoretical Analyses. Chemical Reviews 2017, 117 (4) , 2257-2312. https://doi.org/10.1021/acs.chemrev.6b00313
  3. Takayuki Tanaka and Atsuhiro Osuka . Chemistry of meso-Aryl-Substituted Expanded Porphyrins: Aromaticity and Molecular Twist. Chemical Reviews 2017, 117 (4) , 2584-2640. https://doi.org/10.1021/acs.chemrev.6b00371
  4. William C. McKee, Judy, I. Wu, Henry S. Rzepa, and Paul von Ragué Schleyer . A Hückel Theory Perspective on Möbius Aromaticity. Organic Letters 2013, 15 (13) , 3432-3435. https://doi.org/10.1021/ol401491s
  5. Heike Fliegl and Dage Sundholm . Aromatic Pathways of Porphins, Chlorins, and Bacteriochlorins. The Journal of Organic Chemistry 2012, 77 (7) , 3408-3414. https://doi.org/10.1021/jo300182b
  6. Miquel Torrent-Sucarrat, Josep M. Anglada, and Josep M. Luis . Evaluation of the Nonlinear Optical Properties for Annulenes with Hückel and Möbius Topologies. Journal of Chemical Theory and Computation 2011, 7 (12) , 3935-3943. https://doi.org/10.1021/ct2005424
  7. Steven M. Bachrach and David Stück. DFT Study of Cycloparaphenylenes and Heteroatom-Substituted Nanohoops. The Journal of Organic Chemistry 2010, 75 (19) , 6595-6604. https://doi.org/10.1021/jo101371m
  8. Heike Fliegl, Dage Sundholm, Stefan Taubert and Fabio Pichierri. Aromatic Pathways in Twisted Hexaphyrins. The Journal of Physical Chemistry A 2010, 114 (26) , 7153-7161. https://doi.org/10.1021/jp1021517
  9. Omer Casher Henry S. Rzepa . Using Semantically-Enabled Components for Social Web-Based Scientific Collaborations. 2010,,, 41-63. https://doi.org/10.1021/bk-2010-1060.ch003
  10. Esau Martinez Olmedo, Serguei Fomine. Graphene Nanobelts, Möbius and Higher Order Möbius Strips Formed from Graphene. A Combined CASSCF/DFT Study. Russian Journal of Physical Chemistry A 2019, 93 (4) , 723-729. https://doi.org/10.1134/S0036024419040216
  11. Irene Casademont-Reig, Tatiana Woller, Julia Contreras-García, Mercedes Alonso, Miquel Torrent-Sucarrat, Eduard Matito. New electron delocalization tools to describe the aromaticity in porphyrinoids. Physical Chemistry Chemical Physics 2018, 20 (4) , 2787-2796. https://doi.org/10.1039/C7CP07581B
  12. Juwon Oh, Young Mo Sung, Woojae Kim, Shigeki Mori, Atsuhiro Osuka, Dongho Kim. Aromaticity Reversal in the Lowest Excited Triplet State of Archetypical Möbius Heteroannulenic Systems. Angewandte Chemie 2016, 128 (22) , 6597-6601. https://doi.org/10.1002/ange.201602083
  13. Juwon Oh, Young Mo Sung, Woojae Kim, Shigeki Mori, Atsuhiro Osuka, Dongho Kim. Aromaticity Reversal in the Lowest Excited Triplet State of Archetypical Möbius Heteroannulenic Systems. Angewandte Chemie International Edition 2016, 55 (22) , 6487-6491. https://doi.org/10.1002/anie.201602083
  14. Erjing Wang, Zikai He, Engui Zhao, Luming Meng, Christian Schütt, Jacky W. Y. Lam, Herman H. Y. Sung, Ian D. Williams, Xuhui Huang, Rainer Herges, Ben Zhong Tang. Aggregation-Induced-Emission-Active Macrocycle Exhibiting Analogous Triply and Singly Twisted Möbius Topologies. Chemistry - A European Journal 2015, 21 (33) , 11707-11711. https://doi.org/10.1002/chem.201502224
  15. Gaston R. Schaller, Filip Topić, Kari Rissanen, Yoshio Okamoto, Jun Shen, Rainer Herges. Design and synthesis of the first triply twisted Möbius annulene. Nature Chemistry 2014, 6 (7) , 608-613. https://doi.org/10.1038/nchem.1955
  16. . Fundamentals of Organic Chemistry. 2014,,, 99-195. https://doi.org/10.1002/9781118671191.ch3
  17. Heike Fliegl, Nergiz Özcan, Raul Mera-Adasme, Fabio Pichierri, Jonas Jusélius, Dage Sundholm. Aromatic pathways in thieno-bridged porphyrins: understanding the influence of the direction of the thiophene ring on the aromatic character. Molecular Physics 2013, 111 (9-11) , 1364-1372. https://doi.org/10.1080/00268976.2013.794397
  18. Gaston R. Schaller, Rainer Herges. Möbius molecules with twists and writhes. Chem. Commun. 2013, 49 (13) , 1254-1260. https://doi.org/10.1039/C2CC34763F
  19. Janna Hastings, Despoina Magka, Colin Batchelor, Lian Duan, Robert Stevens, Marcus Ennis, Christoph Steinbeck. Structure-based classification and ontology in chemistry. Journal of Cheminformatics 2012, 4 (1) https://doi.org/10.1186/1758-2946-4-8
  20. Mercedes Alonso, Paul Geerlings, Frank de Proft. Viability of Möbius Topologies in [26]- and [28]Hexaphyrins. Chemistry - A European Journal 2012, 18 (35) , 10916-10928. https://doi.org/10.1002/chem.201200511
  21. Hiroyuki Shima. Persistent current in quantum torus knots. Physical Review B 2012, 86 (3) https://doi.org/10.1103/PhysRevB.86.035415
  22. Chaim Dryzun, David Avnir. Chirality Measures for Vectors, Matrices, Operators and Functions. ChemPhysChem 2011, 12 (1) , 197-205. https://doi.org/10.1002/cphc.201000715
  23. Heike Fliegl, Stefan Taubert, Olli Lehtonen, Dage Sundholm. The gauge including magnetically induced current method. Physical Chemistry Chemical Physics 2011, 13 (46) , 20500. https://doi.org/10.1039/c1cp21812c
  24. Heike Fliegl, Dage Sundholm, Fabio Pichierri. Aromatic pathways in mono- and bisphosphorous singly Möbius twisted [28] and [30]hexaphyrins. Physical Chemistry Chemical Physics 2011, 13 (46) , 20659. https://doi.org/10.1039/c1cp21935a
  25. Evangelos Miliordos. Hückel versus Möbius aromaticity: The particle in a cylinder versus a Möbius strip. Physical Review A 2010, 82 (6) https://doi.org/10.1103/PhysRevA.82.062118
  26. Pablo Rivera-Fuentes, José Lorenzo Alonso-Gómez, Ana G. Petrovic, Paul Seiler, Fabrizio Santoro, Nobuyuki Harada, Nina Berova, Henry S. Rzepa, François Diederich. Enantiomerically Pure Alleno-Acetylenic Macrocycles: Synthesis, Solid-State Structures, Chiroptical Properties, and Electron Localization Function Analysis. Chemistry - A European Journal 2010, 16 (32) , 9796-9807. https://doi.org/10.1002/chem.201001087
  27. Michael Mauksch, Svetlana B. Tsogoeva. Demonstration of “Möbius” Aromaticity in Planar Metallacycles. Chemistry - A European Journal 2010, 16 (26) , 7843-7851. https://doi.org/10.1002/chem.201000396
  28. K. Abersfelder, A. J. P. White, H. S. Rzepa, D. Scheschkewitz. A Tricyclic Aromatic Isomer of Hexasilabenzene. Science 2010, 327 (5965) , 564-566. https://doi.org/10.1126/science.1181771
  29. Steven M. Bachrach. Computational organic chemistry. Annual Reports Section "B" (Organic Chemistry) 2010, 106 , 407. https://doi.org/10.1039/b927078g

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