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 nonaromati...c 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.
Keywords:
benzene / naphthalene / anthracene / Aromaticity / Aromatization / Vehicles / Silicon compounds / Spin delocalizations / Singlet-triplet energy gap / Spin density distributions / Density functional theory / Energy gap / Naphthalene / Silicon compounds / AntiaromaticitySource:
New Journal of Chemistry, 2021, 45, 11, 5060-5074Publisher:
- Royal Society of Chemistry
Funding / projects:
- Ministry of Science, Technological Development and Innovation of the Republic of Serbia, institutional funding - 200168 (University of Belgrade, Faculty of Chemistry) (RS-MESTD-inst-2020-200168)
Note:
- Supplementary information: https://cer.ihtm.bg.ac.rs/handle/123456789/4484
Related info:
- Referenced by
https://cer.ihtm.bg.ac.rs/handle/123456789/4484
DOI: 10.1039/d1nj00207d
ISSN: 1144-0546; 1369-9261
WoS: 000631378900016
Scopus: 2-s2.0-85102960034
Collections
Institution/Community
IHTMTY - JOUR AU - Baranac-Stojanović, Marija AU - Stojanović, Milovan AU - Aleksić, Jovana PY - 2021 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/4483 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 . .