Aromaticity and ring currents in boron-doped porphyrins; New Journal of Chemistry; Vol. 49, iss. 36
| Источник: | New Journal of Chemistry.— .— London: Royal Society of Chemistry Vol. 49, iss. 36.— 2025.— 8 p. |
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| Другие авторы: | , , , |
| Примечания: | Title screen The electron delocalization and aromaticity of a series of boron-doped porphyrins were investigated computationally using the ring current criterion. Magnetically induced current densities, ring current strengths, and aromatic ring current pathways were calculated at the density functional theory (DFT) level using the B3LYP and BHandHLYP functionals. The results demonstrate that boron coordination with O/Cl, as well as two-electron oxidation of B2(porphin) disrupt current pathways, significantly altering the aromatic character and magnetic properties of the molecules. Neutral B2(porphin) sustains a strong paratropic ring current of −39.1 nA T−1 leading to its paramagnetism (χ = 15.6 a.u.). In contrast, its double charged forms adopt aromatic character with diatropic ring current (27.3 nA T−1 and 28.3 nA T−1 for dication and dianion, respectively) and diamagnetic susceptibility (χ = −77.2 a.u. and χ = −88.9 a.u. for dication and dianion, respectively). The introduction of electron-deficient boron atoms into the conjugated system of aromatic porphin and antiaromatic isophlorins reduces electron delocalization, as evidenced by significantly weaker ring current strengths compared to their parent counterparts without boron atoms. Charge-dependent ring current behavior was also observed for meso-boron-doped porphin, tetraoxa-isophlorin, and tetrathia-isophlorin. Notably, the B-tetrathia-isophlorin dication sustains a strong diatropic ring current of 13.1 nA T−1 despite its distorted geometry, confirming its aromatic character. These findings highlight the tunable electronic and magnetic properties of boron-doped porphyrins, providing key insights for designing functional molecular materials Текстовый файл AM_Agreement |
| Язык: | английский |
| Опубликовано: |
2025
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| Предметы: | |
| Online-ссылка: | https://doi.org/10.1039/D5NJ02286J |
| Формат: | Электронный ресурс Статья |
| Запись в KOHA: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=685153 |
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| 200 | 1 | |a Aromaticity and ring currents in boron-doped porphyrins |f Lenara I. Valiulina, R. Valiyev, Victor N. Cherepanova, Elena V. Stepanova | |
| 203 | |a Текст |b визуальный |c электронный | ||
| 283 | |a online_resource |2 RDAcarrier | ||
| 300 | |a Title screen | ||
| 330 | |a The electron delocalization and aromaticity of a series of boron-doped porphyrins were investigated computationally using the ring current criterion. Magnetically induced current densities, ring current strengths, and aromatic ring current pathways were calculated at the density functional theory (DFT) level using the B3LYP and BHandHLYP functionals. The results demonstrate that boron coordination with O/Cl, as well as two-electron oxidation of B2(porphin) disrupt current pathways, significantly altering the aromatic character and magnetic properties of the molecules. Neutral B2(porphin) sustains a strong paratropic ring current of −39.1 nA T−1 leading to its paramagnetism (χ = 15.6 a.u.). In contrast, its double charged forms adopt aromatic character with diatropic ring current (27.3 nA T−1 and 28.3 nA T−1 for dication and dianion, respectively) and diamagnetic susceptibility (χ = −77.2 a.u. and χ = −88.9 a.u. for dication and dianion, respectively). The introduction of electron-deficient boron atoms into the conjugated system of aromatic porphin and antiaromatic isophlorins reduces electron delocalization, as evidenced by significantly weaker ring current strengths compared to their parent counterparts without boron atoms. Charge-dependent ring current behavior was also observed for meso-boron-doped porphin, tetraoxa-isophlorin, and tetrathia-isophlorin. Notably, the B-tetrathia-isophlorin dication sustains a strong diatropic ring current of 13.1 nA T−1 despite its distorted geometry, confirming its aromatic character. These findings highlight the tunable electronic and magnetic properties of boron-doped porphyrins, providing key insights for designing functional molecular materials | ||
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| 461 | 1 | |t New Journal of Chemistry |c London |n Royal Society of Chemistry | |
| 463 | 1 | |t Vol. 49, iss. 36 |v 8 p. |d 2025 | |
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| 701 | 1 | |a Valiulina |b L. |g Lenara | |
| 701 | 1 | |a Valiev |b R. R. |c chemist |c Assistant of Tomsk Polytechnic University |f 1983- |g Rashid Rinatovich |9 17654 | |
| 701 | 1 | |a Cherepanov |b V. N. |g Viktor Nikolaevich | |
| 701 | 1 | |a Stepanova |b E. V. |c chemist |c Associate Professor of Tomsk Polytechnic University, Candidate of Chemical Sciences |f 1988- |g Elena Vladimirovna |9 17776 | |
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