Impact of heteroatoms (S, Se, and Te) on the aromaticity of heterocirculenes /N. N. Karaush-Karmazin, G. V. Baryshnikov, L. I. Valiulina [et al.]

Электронный ресурс
Другой Автор
Baryshnikov, Gleb V.
Valiulina, Lenara I.
Valiev, Rashid R.
Ågren, Hans
Minaev, Boris F.
Karaush-Karmazin, Nataliya N.
Источник
Аннотация
A series of thia[7]circulenes and novel Se-, Te-, S/Te-, and Se/Te-substituted [8]circulenes have been studied by calculations of nucleus-independent chemical shift indices and gauge including magnetically induced currents to interpret the impact of heteroatoms on the aromatic properties of these polyheterocyclic species. The calculations indicate that all the studied hetero[7]circulenes and hetero[8]circulenes consist of two concentric subsystems: an inner seven- or eight-membered core is antiaromatic because of the existence of a paratropic ring current, and an outer system of benzene and hetarene rings that exhibit aromatic behaviour due to the circulation of diatropic ring currents. Thus, most of the hetero[7]circulenes can be considered as slightly antiaromatic because of the slight domination of the paratropic ring currents over the diatropic ones, whereas hetero[8]circulenes represent aromatic species due to the prevailing contribution of the diatropic currents. The antiaromaticity gradually increases with more scattered arrangements of the thiophene and benzene rings in each series of di-, tri-, tetra-, and pentathia[7]circulenes because of the reduced conjugation effect between the neighboring thiophene and benzene rings. Loss of planarity with increased strain leads to an increased antiaromatic character of the lower representatives of the thia[n]circulenes, whereas higher thia[n]circulenes demonstrate a more pronounced aromatic nature because of the small deviation from planarity. The ring current topology is found to be quite insensitive to the heteroatom type, number of hetarene rings and the size of the inner ring; this clearly manifests the special electronic structure of hetero[n]circulenes containing two concentric cyclic subsystems.
Всего оценка: 0
Нет записей для отображения.
 
 
 
03178nab a2200361 c 4500
001
 
 
vtls000673611
003
 
 
RU-ToGU
005
 
 
20200121165100.0
007
 
 
cr |
008
 
 
200116|2019    enk     s         a eng dd
024
7
$a 10.1039/C9NJ02468A $2 doi
035
$a to000673611
039
9
$a 202001211651 $b cat34 $c 202001161559 $d VLOAD $y 202001161550 $z VLOAD
040
$a RU-ToGU $b rus $c RU-ToGU
245
1
0
$a Impact of heteroatoms (S, Se, and Te) on the aromaticity of heterocirculenes $c N. N. Karaush-Karmazin, G. V. Baryshnikov, L. I. Valiulina [et al.]
504
$a Библиогр.: 91 назв.
520
3
$a A series of thia[7]circulenes and novel Se-, Te-, S/Te-, and Se/Te-substituted [8]circulenes have been studied by calculations of nucleus-independent chemical shift indices and gauge including magnetically induced currents to interpret the impact of heteroatoms on the aromatic properties of these polyheterocyclic species. The calculations indicate that all the studied hetero[7]circulenes and hetero[8]circulenes consist of two concentric subsystems: an inner seven- or eight-membered core is antiaromatic because of the existence of a paratropic ring current, and an outer system of benzene and hetarene rings that exhibit aromatic behaviour due to the circulation of diatropic ring currents. Thus, most of the hetero[7]circulenes can be considered as slightly antiaromatic because of the slight domination of the paratropic ring currents over the diatropic ones, whereas hetero[8]circulenes represent aromatic species due to the prevailing contribution of the diatropic currents. The antiaromaticity gradually increases with more scattered arrangements of the thiophene and benzene rings in each series of di-, tri-, tetra-, and pentathia[7]circulenes because of the reduced conjugation effect between the neighboring thiophene and benzene rings. Loss of planarity with increased strain leads to an increased antiaromatic character of the lower representatives of the thia[n]circulenes, whereas higher thia[n]circulenes demonstrate a more pronounced aromatic nature because of the small deviation from planarity. The ring current topology is found to be quite insensitive to the heteroatom type, number of hetarene rings and the size of the inner ring; this clearly manifests the special electronic structure of hetero[n]circulenes containing two concentric cyclic subsystems.
653
$a гетероциркулены
653
$a ароматичность
653
$a гетероатомы
655
4
$a статьи в журналах
700
1
$a Baryshnikov, Gleb V.
700
1
$a Valiulina, Lenara I.
700
1
$a Valiev, Rashid R.
700
1
$a Ågren, Hans
700
1
$a Minaev, Boris F.
700
1
$a Karaush-Karmazin, Nataliya N.
773
0
$t New journal of chemistry $d 2019 $g Vol. 43, № 30. P. 12178-12190 $x 1144-0546 $w to000378339
852
4
$a RU-ToGU
856
4
$u http://vital.lib.tsu.ru/vital/access/manager/Repository/vtls:000673611
908
$a статья
999
$a VIRTUA               
999
$a VTLSSORT0070*0080*0240*0350*0400*2450*5040*5200*6530*6531*6532*6550*7005*7000*7001*7002*7003*7004*7730*8520*8560*9080*9992
Нет комментариев.
Предмет
статьи в журналах
Резюме
A series of thia[7]circulenes and novel Se-, Te-, S/Te-, and Se/Te-substituted [8]circulenes have been studied by calculations of nucleus-independent chemical shift indices and gauge including magnetically induced currents to interpret the impact of heteroatoms on the aromatic properties of these polyheterocyclic species. The calculations indicate that all the studied hetero[7]circulenes and hetero[8]circulenes consist of two concentric subsystems: an inner seven- or eight-membered core is antiaromatic because of the existence of a paratropic ring current, and an outer system of benzene and hetarene rings that exhibit aromatic behaviour due to the circulation of diatropic ring currents. Thus, most of the hetero[7]circulenes can be considered as slightly antiaromatic because of the slight domination of the paratropic ring currents over the diatropic ones, whereas hetero[8]circulenes represent aromatic species due to the prevailing contribution of the diatropic currents. The antiaromaticity gradually increases with more scattered arrangements of the thiophene and benzene rings in each series of di-, tri-, tetra-, and pentathia[7]circulenes because of the reduced conjugation effect between the neighboring thiophene and benzene rings. Loss of planarity with increased strain leads to an increased antiaromatic character of the lower representatives of the thia[n]circulenes, whereas higher thia[n]circulenes demonstrate a more pronounced aromatic nature because of the small deviation from planarity. The ring current topology is found to be quite insensitive to the heteroatom type, number of hetarene rings and the size of the inner ring; this clearly manifests the special electronic structure of hetero[n]circulenes containing two concentric cyclic subsystems.