Aromaticity and Antiaromaticity: Refining Concepts and Expanding Perspectives

A special issue of Chemistry (ISSN 2624-8549). This special issue belongs to the section "Theoretical and Computational Chemistry".

Deadline for manuscript submissions: 20 December 2025 | Viewed by 6489

Special Issue Editors


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Guest Editor
Departamento de Física Aplicada, Cinvestav Mérida, Km. 6 Antigua Carretera a Progreso, Apdo. Postal 73, Cordemex, Mérida 97310, Yuc., México
Interests: theoretical chemistry; aromaticity; boron clusters; potential energy surface; reaction mechanisms

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Guest Editor
Institut de Química Computacional i Catàlisi, Universitat de Girona, C/ M. Aurèlia Capmany, 69, 17003 Girona, Spain
Interests: electron delocalization; aromaticity; reaction mechanisms; carbon nanostructures; excited states
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Guest Editor
Department of Chemistry—Ångström Laboratory, Uppsala University, 751 20 Uppsala, Sweden
Interests: excited-state (anti)aromaticity; organic photochemistry (both experiments and theory); renewable energy; sustainability; urban science

Special Issue Information

Dear Colleagues,

We are pleased to announce a Special Issue of Chemistry on aromaticity, dedicated to exploring and critically assessing this foundational yet evolving concept in chemistry.

Aromaticity remains one of the most widely used but also debated “unicorns” in the chemical sciences (https://onlinelibrary.wiley.com/doi/full/10.1002/jcc.20543). While it provides an essential framework for understanding benzene-like systems, its definition remains subject to diverse interpretations across theoretical and experimental disciplines. This Special Issue will bring together cutting-edge research and conceptual discussions to refine our understanding of aromaticity and antiaromaticity.

Scope and Topics:

This Special Issue will share critical reflections, new theoretical insights, and experimental findings that contribute to shaping the definition and applications of (anti)aromaticity. To ensure a broad and meaningful discussion, we encourage authors to include a dedicated section in their manuscripts presenting their views on the definitions of aromaticity and antiaromaticity.

Submissions may include the following:

  • Conceptual and theoretical (re)analysis and perspectives on aromaticity and antiaromaticity;
  • New experimental and computational approaches to assessing (anti)aromaticity;
  • Applications of (anti)aromatic systems in materials science, catalysis, and beyond;
  • Studies on delocalization, electronic effects, and bonding models;
  • Historical and future perspectives on defining and standardizing aromaticity.

In addition to original research articles, we particularly welcome short reviews and perspective articles that critically examine the current state of the field and provide arguments for potential refinements to the IUPAC definitions of aromaticity and antiaromaticity.

This Special Issue will serve as a platform to extend the discussions initiated at Aromaticity 2025. We invite both conference participants and the broader scientific community to contribute.

We look forward to receiving your contributions and enjoying a thought-provoking discussion on the future of aromaticity.

Please contact the Guest Editors or the journal’s editorial team with any enquiries.

Prof. Dr. Gabriel Merino
Prof. Dr. Miquel Solà
Prof. Dr. Henrik Ottosson
Guest Editors

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Keywords

  • aromaticity
  • delocalization
  • symmetry
  • topology
  • magnetism
  • electronic structure
  • excited states

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Published Papers (3 papers)

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Research

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11 pages, 1547 KB  
Article
Theoretical Analysis of Intermolecular Interactions in Cationic π-Stacked Dimer Models of Antiaromatic Molecules
by Kosei Nishino, Kenji Okada, Ryota Sugimori, Kohei Tada, Ryohei Kishi and Yasutaka Kitagawa
Chemistry 2025, 7(6), 171; https://doi.org/10.3390/chemistry7060171 - 23 Oct 2025
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Abstract
We have theoretically examined the intermolecular interactions in the cationic states of π-stacked dimers of 4nπ antiaromatic molecules. The ground state of face-to-face π-dimer models, consisting of cyclobutadienes (CBDs), was analyzed as a function of the stacking distance (d) for their [...] Read more.
We have theoretically examined the intermolecular interactions in the cationic states of π-stacked dimers of 4nπ antiaromatic molecules. The ground state of face-to-face π-dimer models, consisting of cyclobutadienes (CBDs), was analyzed as a function of the stacking distance (d) for their monocationic and dicationic states using multi-reference second-order perturbation theory. Multi-configurational wavefunction analysis in a diabatic representation was employed to understand the electronic structures of the dimer models in terms of the monomer electron configurations. It is found that the monocationic dimer exhibits a local minimum at about d = 2.4 Å in the ground state, where each monomer is represented by a superposition between neutral triplet and cationic doublet electron configurations. Crossing of the ground and excited states occurs through changing d, which is due to the small energy gap between the highest occupied and lowest unoccupied molecular orbitals of antiaromatic molecules. Full article
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Review

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26 pages, 3163 KB  
Review
Aromaticity and Antiaromaticity: How to Define Them
by Marija Baranac-Stojanović
Chemistry 2025, 7(4), 127; https://doi.org/10.3390/chemistry7040127 - 8 Aug 2025
Viewed by 2389
Abstract
Aromaticity and antiaromaticity are concepts that are often used to explain and predict the physical and chemical properties of cyclic conjugated compounds. They are associated with 4n + 2 and 4n cyclically arranged electrons that are delocalized and mostly localized, respectively. The large [...] Read more.
Aromaticity and antiaromaticity are concepts that are often used to explain and predict the physical and chemical properties of cyclic conjugated compounds. They are associated with 4n + 2 and 4n cyclically arranged electrons that are delocalized and mostly localized, respectively. The large number of papers devoted to these concepts, together with two recent conferences on aromaticity (Aromaticity 2018 and 2025, Mexico) that brought together experts from all over the world to discuss aromaticity and antiaromaticity and their applications testify to their importance, but also to the lack of a simple and easily understandable definition. This review highlights the most important manifestations of (anti)aromaticity by considering selected examples from the literature, chosen to provide us with a clearer picture of these two concepts. Full article
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49 pages, 11537 KB  
Review
Photocyclization of Alkenes and Arenes: Penetrating Through Aromatic Armor with the Help of Excited State Antiaromaticity
by Nikolas R. Dos Santos, Judy I. Wu and Igor V. Alabugin
Chemistry 2025, 7(3), 79; https://doi.org/10.3390/chemistry7030079 - 9 May 2025
Cited by 1 | Viewed by 3138
Abstract
This review focuses on photocyclization reactions involving alkenes and arenes. Photochemistry opens up synthetic opportunities difficult for thermal methods, using light as a versatile tool to convert stable ground-state molecules into their reactive excited counterparts. This difference can be particularly striking for aromatic [...] Read more.
This review focuses on photocyclization reactions involving alkenes and arenes. Photochemistry opens up synthetic opportunities difficult for thermal methods, using light as a versatile tool to convert stable ground-state molecules into their reactive excited counterparts. This difference can be particularly striking for aromatic molecules, which, according to Baird’s rule, transform from highly stable entities into their antiaromatic “evil twins”. We highlight classical reactions, such as the photocyclization of stilbenes, to show how alkenes and aromatic rings can undergo intramolecular cyclizations to form complex structures. When possible, we explain how antiaromaticity develops in excited states and how this can expand synthetic possibilities. The review also examines how factors such as oxidants, substituents, and reaction conditions influence product selectivity, providing useful insights for improving reaction outcomes and demonstrating how photochemical methods can drive the development of new synthetic strategies. Full article
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