Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?

Pino‐Rios, Ricardo; Báez‐Grez, Rodrigo; Solà, Miquel

doi:10.1039/d1cp01441b

Cited by 21 publications

(31 citation statements)

References 79 publications

(49 reference statements)

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“…The diradicaloid character (in all of the compounds for which it is more stable than the closed-shell singlets) reduces the tropicity–diatropicity in the acenes and paratropicity in the STGSNR compounds. The triplet reversed the general tropicity, in accordance with Baird’s aromaticity/antiaromaticity rules. − …”

Section: Results and Discussionsupporting

confidence: 69%

Singlet Fission and Aromaticity

Stanger

2022

J. Phys. Chem. A

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Qualitative aromaticity-based arguments are often used to explain singlet fission (SF) properties in polycyclic conjugated systems. It has been shown by Fowler and collaborators that magnetically induced ring currents are associated with transitions between occupied and unoccupied molecular orbitals (MOs). Since SF has to do with relative energies of electronic states, it was hypothesized that induced currents may indicate SF properties. The quantitative aromaticity of linear oligoacene and several doubly boron-doped anthracenes and phenanthrenes, in their closed-shell singlet, open-shell singlet (where applicable), and triplet electronic states, has been studied using nucleus-independent chemical shift (NICS)-XY scan methods. It is shown that quantitative magnetic aromaticity can be used to identify SF compounds, at least for initial screening. Thus, the induced current features that are indicative of singlet fission (SF) ability have been found to be global current and local current at each ring of the systems. This conclusion was verified for very different systemsa tetracyclic, nitrogen-containing quinone (6), diphenyl benzofurane (7), and cibalackrot (8), all reported to be SF systems. Finally, it is predicted that some isomers of the doubly boron-doped linear[4]phenylene should show SF properties.

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Section: Results and Discussionsupporting

confidence: 69%

Singlet Fission and Aromaticity

Stanger

2022

J. Phys. Chem. A

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“…Test1 (triplet-state pentacene, Fig. 6a) was computationally characterized by Sola `and coworkers 98 and provided an opportunity to test the application of NICS2BC to an open-shell system. Test2 (Fig.…”

Section: Pccp Papermentioning

confidence: 99%

Simple and efficient visualization of aromaticity: bond currents calculated from NICS values

Paenurk

Gershoni‐Poranne

2022

Phys. Chem. Chem. Phys.

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“…As a result, there are multiple all-A PBHs but only one all-L PBH for each isomer family. Among these all-A compounds, polyphenacenes (i.e., “zigzag”-type structures; Figure A and D1) are a specific and well-known subset and have been quite extensively studied. − To the best of our knowledge, however, a systematic study has not been reported on the structure–property relationships of other all-A PBHs or on molecules containing mixtures of A and L motifs.…”

Section: Resultsmentioning

confidence: 99%

Interpretable Deep-Learning Unveils Structure–Property Relationships in Polybenzenoid Hydrocarbons

et al. 2023

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In this work, interpretable deep learning was used to identify structure−property relationships governing the HOMO− LUMO gap and the relative stability of polybenzenoid hydrocarbons (PBHs) using a ring-based graph representation. This representation was combined with a subunit-based perception of PBHs, allowing chemical insights to be presented in terms of intuitive and simple structural motifs. The resulting insights agree with conventional organic chemistry knowledge and electronic structure-based analyses and also reveal new behaviors and identify influential structural motifs. In particular, we evaluated and compared the effects of linear, angular, and branching motifs on these two molecular properties and explored the role of dispersion in mitigating the torsional strain inherent in nonplanar PBHs. Hence, the observed regularities and the proposed analysis contribute to a deeper understanding of the behavior of PBHs and form the foundation for design strategies for new functional PBHs.

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Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?

Abstract: The larger stability of phenacenes compared to their acene isomers in their ground states is attributed to the larger aromaticity of the former. To our knowledge the relative stability of...

Cited by 21 publications

References 79 publications

Singlet Fission and Aromaticity

Singlet Fission and Aromaticity

Simple and efficient visualization of aromaticity: bond currents calculated from NICS values

Interpretable Deep-Learning Unveils Structure–Property Relationships in Polybenzenoid Hydrocarbons

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