Azole-Based Diarylethenes Containing Benzoheteroarene π-Linkers for Solar Thermal Energy Storage: Influence of Aromaticity and Noncovalent Interactions DOI

Thillaiarasi Sukumar,

Mahesh Kumar Ravva, Baswanth Oruganti

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Diarylethene photoswitches featuring azole-based diaryl units combined with benzoheteroarene π-linkers have gained significant research interest in recent years due to their potential achieve higher photocyclization efficiencies compared conventional dithienylethene switches. In this work, we investigate the suitability of these for molecular solar thermal energy storage (MOST) applications through computational modeling electrocyclization and cycloreversion reactions. Our calculations demonstrate that it is possible simultaneously both large energy-storage densities (0.29-0.35 MJ kg-1) prolonged times (half-lives up 124 days) under ambient conditions dithiazolyl dioxazolyl switches containing six distinct π-linkers. Furthermore, isomerization stabilization noncovalent interaction analysis reveal variations between stem from differences aromaticities core π-linker, as well changes interactions. Notably, relative populations photoreactive anti-parallel non-photoreactive parallel conformers ring-open form are governed by weak intramolecular C···C interactions two aryl rings. These findings highlight importance optimizing such enhance MOST systems.

Language: Английский

HOMAc: A Parameterization of the Harmonic Oscillator Model of Aromaticity (HOMA) That Includes Antiaromaticity DOI Creative Commons
Enrique M. Arpa, S. Stafström, Bo Durbeej

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

The harmonic oscillator model of aromaticity (HOMA) offers a straightforward route to quantifying that requires no other information than the bond lengths conjugated ring in question. Given such is often readily obtainable from quantum-chemical calculations, it pertinent improve this parametrized as much possible. Here, new version HOMA presented where, atypically, corresponding parameters are derived actual both aromatic and antiaromatic (rather nonaromatic) reference compounds, calculated with high-level method. resulting model, which we denote HOMAc, covers CC, CN, NN, CO bonds tested at eight different levels theory for 45 (single-ring, multi-ring, carbocyclic, N,O-heterocyclic) molecules across aromatic-antiaromatic spectrum. Thereby, found HOMAc provides description antiaromaticity better accord magnetic, energetic, π-delocalization-based data does standard parametrization HOMA. Altogether, results highlight possibility realize more reliable geometry-based probing (anti)aromaticity use substantial freedom choice

Language: Английский

Citations

2
Azole-Based Diarylethenes Containing Benzoheteroarene π-Linkers for Solar Thermal Energy Storage: Influence of Aromaticity and Noncovalent Interactions DOI

Thillaiarasi Sukumar,

Mahesh Kumar Ravva, Baswanth Oruganti

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Diarylethene photoswitches featuring azole-based diaryl units combined with benzoheteroarene π-linkers have gained significant research interest in recent years due to their potential achieve higher photocyclization efficiencies compared conventional dithienylethene switches. In this work, we investigate the suitability of these for molecular solar thermal energy storage (MOST) applications through computational modeling electrocyclization and cycloreversion reactions. Our calculations demonstrate that it is possible simultaneously both large energy-storage densities (0.29-0.35 MJ kg-1) prolonged times (half-lives up 124 days) under ambient conditions dithiazolyl dioxazolyl switches containing six distinct π-linkers. Furthermore, isomerization stabilization noncovalent interaction analysis reveal variations between stem from differences aromaticities core π-linker, as well changes interactions. Notably, relative populations photoreactive anti-parallel non-photoreactive parallel conformers ring-open form are governed by weak intramolecular C···C interactions two aryl rings. These findings highlight importance optimizing such enhance MOST systems.

Language: Английский

Citations

0