Triplet state (anti)aromaticity of some monoheterocyclic analogues of benzene, naphthalene and anthracene

Baranac‐Stojanović, Marija; Stojanović, Milovan; Aleksić, Jovana

doi:10.1039/d1nj00207d

Cited by 9 publications

(8 citation statements)

References 118 publications

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“…Its triplet state energy is also close to the ideal value of ≥ 1 eV, [25] compared with 1.8 eV in the case of anthracene [24] . In our recent work, [26] we found that silicon substitution in benzene, naphthalene and anthracene most effectively reduced the S 0 −T 1 energy gaps, compared with heteroatoms such as nitrogen, phosphorus, oxygen and sulfur. This result was ascribed to the silicon atom‘s ability to quench the triplet state antiaromaticity of a hydrocarbon, whereas other heteroatoms retained or just reduced it.…”

Section: Introductionsupporting

confidence: 70%

“…Diatropicity of benzene in 1‐silanaphthalene appears to be larger. In our previous work, we showed that spin density localization decreases the extent of global antiaromaticity [26] . The AICD plots shown in Figures S6 and S7 also reveal diatropicity of benzene subunits in 1‐ and 2‐silanaphthalene, larger in the former, but weaker than in their ground states.…”

Section: Resultsmentioning

confidence: 54%

“…in eV: benzene (3.95 [56] /3.8), naphthalene (2.63 [57] /2.7), anthracene (1.87 [57] /1.8), tetracene (1.2 [58] /1.2), phenanthrene (2.7 [59] /2.8) and benz[ a ]anthracene (2.0 [60] /2.1). Also, the B3LYP functional is frequently used to study poly(hetero)cyclic compounds in their excited triplet states and it shows good agreement with other functionals and levels of theory [24,26,37d,61] …”

Section: Resultsmentioning

confidence: 99%

“…Our computational study on silicon‐substituted polycyclic aromatic hydrocarbons (PAHs) was prompted by our recent result on the special behaviour of silicon atom in triplet state heterocycles [26] and led us to the following most important conclusions.…”

Section: Discussionmentioning

confidence: 99%

“…This result was ascribed to the silicon atom‘s ability to quench the triplet state antiaromaticity of a hydrocarbon, whereas other heteroatoms retained or just reduced it. Thus, silabenzene was found to be nonaromatic in its T 1 state, 1‐ and 2‐silanaphthalenes and 9‐silaanthracene weakly aromatic [26] . These results deviate from Baird′s rule stating that (4n+2)/4n π‐electron systems are antiaromatic/aromatic in their first excited triplet state [27] .…”

Section: Introductionmentioning

confidence: 99%

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Revival of Hückel Aromatic (Poly)benzenoid Subunits in Triplet State Polycyclic Aromatic Hydrocarbons by Silicon Substitution

Baranac‐Stojanović

Stojanović

Aleksić

2022

Chemistry An Asian Journal

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By employing density functional theory (DFT) calculations we show that mono‐ and disilicon substitution in polycyclic aromatic hydrocarbons, having two to four benzene units, quenches their triplet state antiaromaticity by creating Hückel aromatic (poly)benzenoid subunit(s) and weakly antiaromatic, or almost nonaromatic silacycle. Therefore, such systems are predicted to be globally aromatic in both the ground state and the first excited triplet state. Putting the silicon atom(s) into various positions of a hydrocarbon provides an opportunity to tune the singlet‐triplet energy gaps. They depend on the global aromaticity degree which, in turn, depends on the type of aromatic carbocyclic subunit(s) and the extent of their aromaticity. On the basis of the set of studied compounds, some preliminary rules on how to regulate the extent of global, semiglobal and local aromaticity are proposed. The results of this work extend the importance of Hückel aromaticity concept to excited triplet states which are usually characterized by the Baird type of (anti)aromaticity.

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Section: Introductionsupporting

confidence: 70%

Section: Resultsmentioning

confidence: 54%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Revival of Hückel Aromatic (Poly)benzenoid Subunits in Triplet State Polycyclic Aromatic Hydrocarbons by Silicon Substitution

Baranac‐Stojanović

Stojanović

Aleksić

2022

Chemistry An Asian Journal

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Heteroatom‐Embedded Approach to Vinylene‐Linked Covalent Organic Frameworks with Isoelectronic Structures for Photoredox Catalysis

Meng

et al. 2021

Angewandte Chemie

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Embedding heteroatoms into the main backbones of polymeric materials has become an efficient tool for tailoring their structures and improving their properties. However, owing to comparatively harsh heteroatom‐doping conditions, this has rarely been explored in covalent organic frameworks (COFs). Herein, upon aldol condensation of a trimethyl‐substituted pyrylium salt with a tritopic aromatic aldehyde, a two‐dimensional oxonium‐embedded COF with vinylene linkages was achieved, which was further converted to a neutral pyridine‐cored COF by in situ replacement of oxonium ions with nitrogen atoms under ammonia treatment. The two heteroatom‐embedded COFs are conceptually isoelectronic with each other, featuring similar geometric structures but different electronic structures, rendering them capable of catalyzing the visible‐light‐promoted multi‐component synthesis of tri‐substituted pyridine derivatives with good recyclability.

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Heteroatom‐Embedded Approach to Vinylene‐Linked Covalent Organic Frameworks with Isoelectronic Structures for Photoredox Catalysis

et al. 2021

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Embedding heteroatoms into the main backbones of polymeric materials has become an efficient tool for tailoring their structures and improving their properties.H owever, owingt oc omparatively harsh heteroatom-doping conditions, this has rarely been explored in covalent organic frameworks (COFs). Herein, upon aldol condensation of at rimethylsubstituted pyrylium salt with at ritopic aromatic aldehyde, at wo-dimensional oxonium-embedded COF with vinylene linkages was achieved, which was further converted to aneutral pyridine-cored COF by in situ replacement of oxonium ions with nitrogen atoms under ammonia treatment. The two heteroatom-embedded COFs are conceptually isoelectronic with each other,f eaturing similar geometric structures but different electronic structures,r endering them capable of catalyzing the visible-light-promoted multi-component synthesis of tri-substituted pyridine derivatives with good recyclability.

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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, S) derived from benzene, naphthalene and anthracene, was studied by employing energetic,...

Cited by 9 publications

References 118 publications

Revival of Hückel Aromatic (Poly)benzenoid Subunits in Triplet State Polycyclic Aromatic Hydrocarbons by Silicon Substitution

Revival of Hückel Aromatic (Poly)benzenoid Subunits in Triplet State Polycyclic Aromatic Hydrocarbons by Silicon Substitution

Heteroatom‐Embedded Approach to Vinylene‐Linked Covalent Organic Frameworks with Isoelectronic Structures for Photoredox Catalysis

Heteroatom‐Embedded Approach to Vinylene‐Linked Covalent Organic Frameworks with Isoelectronic Structures for Photoredox Catalysis

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