TY - JOUR
T1 - Origin of Optoelectronic Contradictions in 3,4-Cycloalkyl[c]-chalcogenophenes
T2 - A Computational Study
AU - Masilamani, Ganesh
AU - Krishna, Gamidi Rama
AU - Debnath, Sashi
AU - Bedi, Anjan
N1 - Publisher Copyright:
© 2023 by the authors.
PY - 2023/11
Y1 - 2023/11
N2 - The planar morphology of the backbone significantly contributes to the subtle optoelectronic features of π-conjugated polymers. On the other hand, the atomistic tuning of an otherwise identical π-backbone could also impact optoelectronic properties systematically. In this manuscript, we compare a series of 3,4-cycloalkylchalcogenophenes by tuning them atomistically using group-16 elements. Additionally, the effect of systematically extending these building blocks in the form of oligomers and polymers is studied. The size of the 3,4-substitution affected the morphology of the oligomers. In addition, the heteroatoms contributed to a further alteration in their geometry and resultant optoelectronic properties. The chalcogenophenes, containing smaller 3,4-cycloalkanes, resulted in lower bandgap oligomers or polymers compared to those with larger 3,4-cycloalkanes. Natural bonding orbital (NBO) calculations were performed to understand the disparity alongside the contour maps of frontier molecular orbitals (FMO).
AB - The planar morphology of the backbone significantly contributes to the subtle optoelectronic features of π-conjugated polymers. On the other hand, the atomistic tuning of an otherwise identical π-backbone could also impact optoelectronic properties systematically. In this manuscript, we compare a series of 3,4-cycloalkylchalcogenophenes by tuning them atomistically using group-16 elements. Additionally, the effect of systematically extending these building blocks in the form of oligomers and polymers is studied. The size of the 3,4-substitution affected the morphology of the oligomers. In addition, the heteroatoms contributed to a further alteration in their geometry and resultant optoelectronic properties. The chalcogenophenes, containing smaller 3,4-cycloalkanes, resulted in lower bandgap oligomers or polymers compared to those with larger 3,4-cycloalkanes. Natural bonding orbital (NBO) calculations were performed to understand the disparity alongside the contour maps of frontier molecular orbitals (FMO).
KW - DFT calculation
KW - chalcogenophene
KW - morphology
KW - optoelectronic properties
KW - steric effect
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U2 - 10.3390/polym15214240
DO - 10.3390/polym15214240
M3 - Article
C2 - 37959920
AN - SCOPUS:85176498592
SN - 2073-4360
VL - 15
JO - Polymers
JF - Polymers
IS - 21
M1 - 4240
ER -