When are Antiaromatic Molecules Paramagnetic?; Journal of Physical Chemistry C; Vol. 124, iss. 38
| Parent link: | Journal of Physical Chemistry C Vol. 124, iss. 38.— 2020.— [P. 21027–21035] |
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| Yhteisötekijä: | |
| Muut tekijät: | , , , , |
| Yhteenveto: | Title screen Magnetizabilities and magnetically induced current densities have been calculated and analyzed for a series of antiaromatic cyclo[4k]carbons (k = 2−11), iso[n]phlorins (n = 4−8), expanded porphyrinoids, and meso−meso, β−β, β−β triple-linked porphyrin and isophlorin arrays. The cyclo[4k]carbons with k = 2−6 are predicted to be closed-shell paramagnetic molecules due to the very strong paratropic ring current combined with its large radius. Larger cyclo[4k]carbons with k = 6−11 are diamagnetic because they sustain a paratropic ring current whose strength is weaker than −20 nA T−1 , which seems to be the lower threshold value for closed-shell paramagnetism. This holds not only for cyclo[4k]carbons but also for other organic molecules like expanded porphyrinoids and oligomers of porphyrinoids. The present study shows that meso− meso, β−β, β−β triple-linked linear porphyrin and isophlorin arrays have a domainlike distribution of alternating diatropic and paratropic ring currents. The strength of their local paratropic ring currents is weaker than −20 nA T−1 in each domain. Therefore, linear porphyrin and isophlorin arrays become more diamagnetic with increasing length of the ribbon. For the same reason, squareshaped meso−meso, β−β, β−β triple-linked free-base porphyrin and isophlorin tetramers as well as the Zn(II) complex of the porphyrin tetramer are diamagnetic. We show that closed-shell molecules with large positive magnetizabilities can be designed by following the principle that a strong paratropic current ring combined with a large ring-current radius leads to closed-shell paramagnetism. Режим доступа: по договору с организацией-держателем ресурса |
| Kieli: | englanti |
| Julkaistu: |
2020
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| Aiheet: | |
| Linkit: | https://doi.org/10.1021/acs.jpcc.0c01559 |
| Aineistotyyppi: | Elektroninen Kirjan osa |
| KOHA link: | https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=662868 |
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| 200 | 1 | |a When are Antiaromatic Molecules Paramagnetic? |f R. R. Valiev, G. V. Baryshnikov, R. T. Nasibullin [et al.] | |
| 203 | |a Text |c electronic | ||
| 300 | |a Title screen | ||
| 320 | |a [References: 66 tit.] | ||
| 330 | |a Magnetizabilities and magnetically induced current densities have been calculated and analyzed for a series of antiaromatic cyclo[4k]carbons (k = 2−11), iso[n]phlorins (n = 4−8), expanded porphyrinoids, and meso−meso, β−β, β−β triple-linked porphyrin and isophlorin arrays. The cyclo[4k]carbons with k = 2−6 are predicted to be closed-shell paramagnetic molecules due to the very strong paratropic ring current combined with its large radius. Larger cyclo[4k]carbons with k = 6−11 are diamagnetic because they sustain a paratropic ring current whose strength is weaker than −20 nA T−1 , which seems to be the lower threshold value for closed-shell paramagnetism. This holds not only for cyclo[4k]carbons but also for other organic molecules like expanded porphyrinoids and oligomers of porphyrinoids. The present study shows that meso− meso, β−β, β−β triple-linked linear porphyrin and isophlorin arrays have a domainlike distribution of alternating diatropic and paratropic ring currents. The strength of their local paratropic ring currents is weaker than −20 nA T−1 in each domain. Therefore, linear porphyrin and isophlorin arrays become more diamagnetic with increasing length of the ribbon. For the same reason, squareshaped meso−meso, β−β, β−β triple-linked free-base porphyrin and isophlorin tetramers as well as the Zn(II) complex of the porphyrin tetramer are diamagnetic. We show that closed-shell molecules with large positive magnetizabilities can be designed by following the principle that a strong paratropic current ring combined with a large ring-current radius leads to closed-shell paramagnetism. | ||
| 333 | |a Режим доступа: по договору с организацией-держателем ресурса | ||
| 461 | |t Journal of Physical Chemistry C | ||
| 463 | |t Vol. 124, iss. 38 |v [P. 21027–21035] |d 2020 | ||
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| 701 | 1 | |a Baryshnikov |b G. V. | |
| 701 | 1 | |a Nasibullin |b R. T. |g Rinat | |
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| 701 | 1 | |a Agren |b H. |g Hans | |
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