Triplet state (anti)aromaticity of some monoheterocyclic analogues of benzene, naphthalene and anthracene
Abstract
Aromaticity–antiaromaticity switch upon singlet–triplet transition of some biologically and synthetically important monoheterocycles (heteroatom = N, O, Si, P, and S) derived from benzene, naphthalene and anthracene was studied by employing energetic, magnetic and structural aromaticity criteria, at the density functional theory (DFT) level. The relationship between spin density distribution, (anti)aromaticity and singlet–triplet energy gaps, in the studied molecules, was found. In general, spin delocalization results in antiaromaticity, spin density localization to one ring in bi- and tricycles localizes antiaromaticity and spin localization on a heteroatom reduces global and local antiaromaticity. The latter reaches nonaromaticity in the case of silicon atoms which have larger orbitals and show more tendency to accept unpaired electrons. Spin density localization in bi- and tricycles allows benzene subunit(s) to develop local aromaticity, which, when combined with nonaromatic silacyc...le and weak global antiaromaticity, results in overall triplet state weak aromaticity. The singlet–triplet energy gaps decrease with a decrease in the triplet state antiaromaticity and are the lowest for silicon-containing compounds.
Source:
New Journal of Chemistry, 2021, 45, 11, 5060-5074Publisher:
- Royal Society of Chemistry
Funding / projects:
Note:
- Supplementary material: https://cherry.chem.bg.ac.rs/handle/123456789/4356
Related info:
- Version of
https://doi.org/10.1039/D1NJ00207D - Referenced by
https://cherry.chem.bg.ac.rs/handle/123456789/4356
DOI: 10.1039/D1NJ00207D
ISSN: 1144-0546
WoS: 000631378900016
Scopus: 2-s2.0-85102960034
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Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Baranac-Stojanović, Marija AU - Stojanović, Milovan AU - Aleksić, Jovana PY - 2021 UR - https://cherry.chem.bg.ac.rs/handle/123456789/4355 AB - Aromaticity–antiaromaticity switch upon singlet–triplet transition of some biologically and synthetically important monoheterocycles (heteroatom = N, O, Si, P, and S) derived from benzene, naphthalene and anthracene was studied by employing energetic, magnetic and structural aromaticity criteria, at the density functional theory (DFT) level. The relationship between spin density distribution, (anti)aromaticity and singlet–triplet energy gaps, in the studied molecules, was found. In general, spin delocalization results in antiaromaticity, spin density localization to one ring in bi- and tricycles localizes antiaromaticity and spin localization on a heteroatom reduces global and local antiaromaticity. The latter reaches nonaromaticity in the case of silicon atoms which have larger orbitals and show more tendency to accept unpaired electrons. Spin density localization in bi- and tricycles allows benzene subunit(s) to develop local aromaticity, which, when combined with nonaromatic silacycle and weak global antiaromaticity, results in overall triplet state weak aromaticity. The singlet–triplet energy gaps decrease with a decrease in the triplet state antiaromaticity and are the lowest for silicon-containing compounds. PB - Royal Society of Chemistry T2 - New Journal of Chemistry T1 - Triplet state (anti)aromaticity of some monoheterocyclic analogues of benzene, naphthalene and anthracene VL - 45 IS - 11 SP - 5060 EP - 5074 DO - 10.1039/D1NJ00207D ER -
@article{ author = "Baranac-Stojanović, Marija and Stojanović, Milovan and Aleksić, Jovana", year = "2021", abstract = "Aromaticity–antiaromaticity switch upon singlet–triplet transition of some biologically and synthetically important monoheterocycles (heteroatom = N, O, Si, P, and S) derived from benzene, naphthalene and anthracene was studied by employing energetic, magnetic and structural aromaticity criteria, at the density functional theory (DFT) level. The relationship between spin density distribution, (anti)aromaticity and singlet–triplet energy gaps, in the studied molecules, was found. In general, spin delocalization results in antiaromaticity, spin density localization to one ring in bi- and tricycles localizes antiaromaticity and spin localization on a heteroatom reduces global and local antiaromaticity. The latter reaches nonaromaticity in the case of silicon atoms which have larger orbitals and show more tendency to accept unpaired electrons. Spin density localization in bi- and tricycles allows benzene subunit(s) to develop local aromaticity, which, when combined with nonaromatic silacycle and weak global antiaromaticity, results in overall triplet state weak aromaticity. The singlet–triplet energy gaps decrease with a decrease in the triplet state antiaromaticity and are the lowest for silicon-containing compounds.", publisher = "Royal Society of Chemistry", journal = "New Journal of Chemistry", title = "Triplet state (anti)aromaticity of some monoheterocyclic analogues of benzene, naphthalene and anthracene", volume = "45", number = "11", pages = "5060-5074", doi = "10.1039/D1NJ00207D" }
Baranac-Stojanović, M., Stojanović, M.,& Aleksić, J.. (2021). Triplet state (anti)aromaticity of some monoheterocyclic analogues of benzene, naphthalene and anthracene. in New Journal of Chemistry Royal Society of Chemistry., 45(11), 5060-5074. https://doi.org/10.1039/D1NJ00207D
Baranac-Stojanović M, Stojanović M, Aleksić J. Triplet state (anti)aromaticity of some monoheterocyclic analogues of benzene, naphthalene and anthracene. in New Journal of Chemistry. 2021;45(11):5060-5074. doi:10.1039/D1NJ00207D .
Baranac-Stojanović, Marija, Stojanović, Milovan, Aleksić, Jovana, "Triplet state (anti)aromaticity of some monoheterocyclic analogues of benzene, naphthalene and anthracene" in New Journal of Chemistry, 45, no. 11 (2021):5060-5074, https://doi.org/10.1039/D1NJ00207D . .