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The effect of two types of dibenzoannulation of pentalene on molecular energies and magnetically induced currents

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2019
Authors
Baranac-Stojanović, Marija
Stojanović, Milovan
Article (Published version)
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Abstract
The effect of two types of dibenzo-fusion of pentalene in the singlet and triplet states on its molecular energies and magnetically induced ring currents was examined via density functional calculations. The isomerization energy decomposition analysis (IEDA) together with the calculated aromaticity indices (NICS(1) zz , HOMA and FLU π ), estimation of resonance energies (RE) and extra cyclic resonance energies (ECRE) via the NBO method, and the NICS-XY-scans revealed that the π-electronic system is the most important factor controlling the molecular energies. The [a,f] topology features greater delocalization, which results in two opposing effects: larger ECRE, but weaker π-bonding. The latter is mainly responsible for the higher energy of [a,f]-dibenzopentalene (DBP) (ΔE iso = 21.7 kcal mol -1 ), with the other effects being σ-orbital and electrostatic interactions. The reversal of energetic stability in the triplet states (ΔE iso = -10.8 kcal mol -1 ) mainly comes from the reduced Pa...uli repulsion in [a,f]-DBP, which stabilizes the unpaired spin density over the central trimethylenemethane subunit vs. the central pentalene subunit in [a,e]-DBP. Although the [a,e] topology only reduces the diatropic and paratropic currents of the elementary subunits, benzene and pentalene, the [a,f] topology also creates strong global paratropicity involving the benzene rings. Both DBP isomers are characterized by global and smaller semi-global and local diatropic currents in the triplet state.

Keywords:
Cascade carbopalladation reaction / Excited-state aromaticity / Chemical-shifts nics / Ground-state / Electron delocalization / Quantum contributions / Antiaromaticity / Benzene / Ring / Derivatives
Source:
Physical Chemistry Chemical Physics, 2019, 21, 6, 3250-3263
Publisher:
  • Royal Society of Chemistry
Funding / projects:
  • Experimental and theoretical study of reactivity and biological activity of stereodefined thiazolidines and their synthetic analogues (RS-172020)
Note:
  • Peer-reviewed manuscript: http://cer.ihtm.bg.ac.rs/handle/123456789/2961

DOI: 10.1039/c8cp07875k

ISSN: 1463-9076

WoS: 000459584900041

Scopus: 2-s2.0-85061118631
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URI
https://cer.ihtm.bg.ac.rs/handle/123456789/2960
Collections
  • Radovi istraživača / Researchers' publications
Institution/Community
IHTM
TY  - JOUR
AU  - Baranac-Stojanović, Marija
AU  - Stojanović, Milovan
PY  - 2019
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/2960
AB  - The effect of two types of dibenzo-fusion of pentalene in the singlet and triplet states on its molecular energies and magnetically induced ring currents was examined via density functional calculations. The isomerization energy decomposition analysis (IEDA) together with the calculated aromaticity indices (NICS(1) zz , HOMA and FLU π ), estimation of resonance energies (RE) and extra cyclic resonance energies (ECRE) via the NBO method, and the NICS-XY-scans revealed that the π-electronic system is the most important factor controlling the molecular energies. The [a,f] topology features greater delocalization, which results in two opposing effects: larger ECRE, but weaker π-bonding. The latter is mainly responsible for the higher energy of [a,f]-dibenzopentalene (DBP) (ΔE iso = 21.7 kcal mol -1 ), with the other effects being σ-orbital and electrostatic interactions. The reversal of energetic stability in the triplet states (ΔE iso = -10.8 kcal mol -1 ) mainly comes from the reduced Pauli repulsion in [a,f]-DBP, which stabilizes the unpaired spin density over the central trimethylenemethane subunit vs. the central pentalene subunit in [a,e]-DBP. Although the [a,e] topology only reduces the diatropic and paratropic currents of the elementary subunits, benzene and pentalene, the [a,f] topology also creates strong global paratropicity involving the benzene rings. Both DBP isomers are characterized by global and smaller semi-global and local diatropic currents in the triplet state.
PB  - Royal Society of Chemistry
T2  - Physical Chemistry Chemical Physics
T1  - The effect of two types of dibenzoannulation of pentalene on molecular energies and magnetically induced currents
VL  - 21
IS  - 6
SP  - 3250
EP  - 3263
DO  - 10.1039/c8cp07875k
ER  - 
@article{
author = "Baranac-Stojanović, Marija and Stojanović, Milovan",
year = "2019",
abstract = "The effect of two types of dibenzo-fusion of pentalene in the singlet and triplet states on its molecular energies and magnetically induced ring currents was examined via density functional calculations. The isomerization energy decomposition analysis (IEDA) together with the calculated aromaticity indices (NICS(1) zz , HOMA and FLU π ), estimation of resonance energies (RE) and extra cyclic resonance energies (ECRE) via the NBO method, and the NICS-XY-scans revealed that the π-electronic system is the most important factor controlling the molecular energies. The [a,f] topology features greater delocalization, which results in two opposing effects: larger ECRE, but weaker π-bonding. The latter is mainly responsible for the higher energy of [a,f]-dibenzopentalene (DBP) (ΔE iso = 21.7 kcal mol -1 ), with the other effects being σ-orbital and electrostatic interactions. The reversal of energetic stability in the triplet states (ΔE iso = -10.8 kcal mol -1 ) mainly comes from the reduced Pauli repulsion in [a,f]-DBP, which stabilizes the unpaired spin density over the central trimethylenemethane subunit vs. the central pentalene subunit in [a,e]-DBP. Although the [a,e] topology only reduces the diatropic and paratropic currents of the elementary subunits, benzene and pentalene, the [a,f] topology also creates strong global paratropicity involving the benzene rings. Both DBP isomers are characterized by global and smaller semi-global and local diatropic currents in the triplet state.",
publisher = "Royal Society of Chemistry",
journal = "Physical Chemistry Chemical Physics",
title = "The effect of two types of dibenzoannulation of pentalene on molecular energies and magnetically induced currents",
volume = "21",
number = "6",
pages = "3250-3263",
doi = "10.1039/c8cp07875k"
}
Baranac-Stojanović, M.,& Stojanović, M.. (2019). The effect of two types of dibenzoannulation of pentalene on molecular energies and magnetically induced currents. in Physical Chemistry Chemical Physics
Royal Society of Chemistry., 21(6), 3250-3263.
https://doi.org/10.1039/c8cp07875k
Baranac-Stojanović M, Stojanović M. The effect of two types of dibenzoannulation of pentalene on molecular energies and magnetically induced currents. in Physical Chemistry Chemical Physics. 2019;21(6):3250-3263.
doi:10.1039/c8cp07875k .
Baranac-Stojanović, Marija, Stojanović, Milovan, "The effect of two types of dibenzoannulation of pentalene on molecular energies and magnetically induced currents" in Physical Chemistry Chemical Physics, 21, no. 6 (2019):3250-3263,
https://doi.org/10.1039/c8cp07875k . .

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