A DFT Study of the Modulation of the Antiaromatic and Open-Shell Character of Dibenzo[a,f]pentalene by Employing Three Strategies: Additional Benzoannulation, BN/CC Isosterism, and Substitution
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2019
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Dibenzo[a,f]pentalene ([a,f]DBP) is a highly antiaromatic molecule having appreciable open-shell singlet character in its ground state. In this work, DFT calculations at the B3LYP/6-311+G(d,p) level of theory were performed to explore the efficiency of three strategies, that is, BN/CC isosterism, substitution, and (di)benzoannulation of [a,f]DBP, in controlling its electronic state and (anti)aromaticity. To evaluate the type and extent of the latter, the harmonic oscillator model of aromaticity (HOMA) and aromatic fluctuation (FLU) indices were used, along with the nucleus-independent chemical shift NICS-XY-scan procedure. The results suggest that all three strategies could be employed to produce either the closed-shell system or open-shell species, which may be in the singlet or triplet ground state. Triplet states have been characterized as aromatic, which is in accordance with Baird's rule. All the singlet states were found to have weaker global paratropicity than [a,f]DBP. Addition...al (di)benzo fusion adds local aromatic subunit(s) and mainly retains the topology of the paratropic ring currents of the basic molecule. The substitution of two carbon atoms by the isoelectronic BN pair, or the introduction of substituents, results either in the same type and very similar topology of ring currents as in the parent compound, or leads to (anti)aromatic and nonaromatic subunits. The triplet states of all the examined compounds are also discussed.
Ključne reči:
aromaticity / density functional calculations / electronic structure / fused-ring systems / substituent effectsIzvor:
Chemistry - A European Journal, 2019, 25, 41, 9747-9757Izdavač:
- Wiley
Finansiranje / projekti:
- Eksperimentalna i teorijska proučavanja reaktivnosti i biološka aktivnost stereodefinisanih tiazolidina i sintetičkih analoga (RS-MESTD-Basic Research (BR or ON)-172020)
Napomena:
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3291
DOI: 10.1002/chem.201901845
ISSN: 0947-6539
WoS: 000476851000001
Scopus: 2-s2.0-85068929725
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Institucija/grupa
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Baranac-Stojanović, Marija PY - 2019 UR - https://cherry.chem.bg.ac.rs/handle/123456789/3826 AB - Dibenzo[a,f]pentalene ([a,f]DBP) is a highly antiaromatic molecule having appreciable open-shell singlet character in its ground state. In this work, DFT calculations at the B3LYP/6-311+G(d,p) level of theory were performed to explore the efficiency of three strategies, that is, BN/CC isosterism, substitution, and (di)benzoannulation of [a,f]DBP, in controlling its electronic state and (anti)aromaticity. To evaluate the type and extent of the latter, the harmonic oscillator model of aromaticity (HOMA) and aromatic fluctuation (FLU) indices were used, along with the nucleus-independent chemical shift NICS-XY-scan procedure. The results suggest that all three strategies could be employed to produce either the closed-shell system or open-shell species, which may be in the singlet or triplet ground state. Triplet states have been characterized as aromatic, which is in accordance with Baird's rule. All the singlet states were found to have weaker global paratropicity than [a,f]DBP. Additional (di)benzo fusion adds local aromatic subunit(s) and mainly retains the topology of the paratropic ring currents of the basic molecule. The substitution of two carbon atoms by the isoelectronic BN pair, or the introduction of substituents, results either in the same type and very similar topology of ring currents as in the parent compound, or leads to (anti)aromatic and nonaromatic subunits. The triplet states of all the examined compounds are also discussed. PB - Wiley T2 - Chemistry - A European Journal T1 - A DFT Study of the Modulation of the Antiaromatic and Open-Shell Character of Dibenzo[a,f]pentalene by Employing Three Strategies: Additional Benzoannulation, BN/CC Isosterism, and Substitution VL - 25 IS - 41 SP - 9747 EP - 9757 DO - 10.1002/chem.201901845 ER -
@article{ author = "Baranac-Stojanović, Marija", year = "2019", abstract = "Dibenzo[a,f]pentalene ([a,f]DBP) is a highly antiaromatic molecule having appreciable open-shell singlet character in its ground state. In this work, DFT calculations at the B3LYP/6-311+G(d,p) level of theory were performed to explore the efficiency of three strategies, that is, BN/CC isosterism, substitution, and (di)benzoannulation of [a,f]DBP, in controlling its electronic state and (anti)aromaticity. To evaluate the type and extent of the latter, the harmonic oscillator model of aromaticity (HOMA) and aromatic fluctuation (FLU) indices were used, along with the nucleus-independent chemical shift NICS-XY-scan procedure. The results suggest that all three strategies could be employed to produce either the closed-shell system or open-shell species, which may be in the singlet or triplet ground state. Triplet states have been characterized as aromatic, which is in accordance with Baird's rule. All the singlet states were found to have weaker global paratropicity than [a,f]DBP. Additional (di)benzo fusion adds local aromatic subunit(s) and mainly retains the topology of the paratropic ring currents of the basic molecule. The substitution of two carbon atoms by the isoelectronic BN pair, or the introduction of substituents, results either in the same type and very similar topology of ring currents as in the parent compound, or leads to (anti)aromatic and nonaromatic subunits. The triplet states of all the examined compounds are also discussed.", publisher = "Wiley", journal = "Chemistry - A European Journal", title = "A DFT Study of the Modulation of the Antiaromatic and Open-Shell Character of Dibenzo[a,f]pentalene by Employing Three Strategies: Additional Benzoannulation, BN/CC Isosterism, and Substitution", volume = "25", number = "41", pages = "9747-9757", doi = "10.1002/chem.201901845" }
Baranac-Stojanović, M.. (2019). A DFT Study of the Modulation of the Antiaromatic and Open-Shell Character of Dibenzo[a,f]pentalene by Employing Three Strategies: Additional Benzoannulation, BN/CC Isosterism, and Substitution. in Chemistry - A European Journal Wiley., 25(41), 9747-9757. https://doi.org/10.1002/chem.201901845
Baranac-Stojanović M. A DFT Study of the Modulation of the Antiaromatic and Open-Shell Character of Dibenzo[a,f]pentalene by Employing Three Strategies: Additional Benzoannulation, BN/CC Isosterism, and Substitution. in Chemistry - A European Journal. 2019;25(41):9747-9757. doi:10.1002/chem.201901845 .
Baranac-Stojanović, Marija, "A DFT Study of the Modulation of the Antiaromatic and Open-Shell Character of Dibenzo[a,f]pentalene by Employing Three Strategies: Additional Benzoannulation, BN/CC Isosterism, and Substitution" in Chemistry - A European Journal, 25, no. 41 (2019):9747-9757, https://doi.org/10.1002/chem.201901845 . .