Abstract
Recently, a family of conducting polyselenophenes was synthesized, and they were shown to have a number of interesting properties. Here we have studied oligoselenophenes, their cation radicals and dications up to the 50-mer (50Se), as well as polyselenophene at the B3LYP/6-31G(d) level of theory, and compared them with the corresponding oligothiophenes. Although the calculations reveal many similarities between oligo- and polyselenophenes and their thiophene-based counterparts, they also show the important differences between those two types of conjugated systems. Oligo- and polyselenophenes have a more quinoid character, lower band gap, and importantly, they are more difficult to twist. The theoretical results suggest that the HOMO-LUMO gap (band gap), bond-length alternation (BLA), and charge distribution in oligo- and polyselenophenes are strongly dependent on inter-ring twisting, yet twisting costs little energy. The inter-ring distances in oligo- and polyselenophenes are shorter than the related distances in oligothiophenes, whereas the bond lengths within the selenophene rings are comparable to those of the corresponding oligothiophenes.
| Original language | English |
|---|---|
| Pages (from-to) | 8613-8624 |
| Number of pages | 12 |
| Journal | Chemistry - A European Journal |
| Volume | 15 |
| Issue number | 34 |
| DOIs | |
| Publication status | Published - Aug 24 2009 |
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Keywords
- Density functional calculations
- Oligoselenophenes
- Polymers
- Polyselenophenes
- Selenium
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Oligo- and polyselenophenes : A theoretical study. / Zade, Sanjio S.; Zamoshchik, Natalia; Bendikov, Michael.
In: Chemistry - A European Journal, Vol. 15, No. 34, 24.08.2009, p. 8613-8624.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Oligo- and polyselenophenes
T2 - A theoretical study
AU - Zade, Sanjio S.
AU - Zamoshchik, Natalia
AU - Bendikov, Michael
PY - 2009/8/24
Y1 - 2009/8/24
N2 - Recently, a family of conducting polyselenophenes was synthesized, and they were shown to have a number of interesting properties. Here we have studied oligoselenophenes, their cation radicals and dications up to the 50-mer (50Se), as well as polyselenophene at the B3LYP/6-31G(d) level of theory, and compared them with the corresponding oligothiophenes. Although the calculations reveal many similarities between oligo- and polyselenophenes and their thiophene-based counterparts, they also show the important differences between those two types of conjugated systems. Oligo- and polyselenophenes have a more quinoid character, lower band gap, and importantly, they are more difficult to twist. The theoretical results suggest that the HOMO-LUMO gap (band gap), bond-length alternation (BLA), and charge distribution in oligo- and polyselenophenes are strongly dependent on inter-ring twisting, yet twisting costs little energy. The inter-ring distances in oligo- and polyselenophenes are shorter than the related distances in oligothiophenes, whereas the bond lengths within the selenophene rings are comparable to those of the corresponding oligothiophenes.
AB - Recently, a family of conducting polyselenophenes was synthesized, and they were shown to have a number of interesting properties. Here we have studied oligoselenophenes, their cation radicals and dications up to the 50-mer (50Se), as well as polyselenophene at the B3LYP/6-31G(d) level of theory, and compared them with the corresponding oligothiophenes. Although the calculations reveal many similarities between oligo- and polyselenophenes and their thiophene-based counterparts, they also show the important differences between those two types of conjugated systems. Oligo- and polyselenophenes have a more quinoid character, lower band gap, and importantly, they are more difficult to twist. The theoretical results suggest that the HOMO-LUMO gap (band gap), bond-length alternation (BLA), and charge distribution in oligo- and polyselenophenes are strongly dependent on inter-ring twisting, yet twisting costs little energy. The inter-ring distances in oligo- and polyselenophenes are shorter than the related distances in oligothiophenes, whereas the bond lengths within the selenophene rings are comparable to those of the corresponding oligothiophenes.
KW - Density functional calculations
KW - Oligoselenophenes
KW - Polymers
KW - Polyselenophenes
KW - Selenium
UR - http://www.scopus.com/inward/record.url?scp=69249127911&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=69249127911&partnerID=8YFLogxK
U2 - 10.1002/chem.200900971
DO - 10.1002/chem.200900971
M3 - Article
C2 - 19658134
AN - SCOPUS:69249127911
VL - 15
SP - 8613
EP - 8624
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 34
ER -