Charge-transfer dynamics in bowl-shaped imide-functionalized corannulenes at ensemble and single-molecule levels
- 1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER TVM) Maruthamala P. O., Vithura Thiruvananthapuram 695551 Kerala India
- 2Institut für Organische Chemie, Center for Nanosystems Chemistry (CNC), Universität Würzburg Am Hubland 97074 Würzburg Germany
Abstract
Curved aromatic hydrocarbons provide unique platforms for tailoring charge-transfer (CT) excited states for functional optoelectronic and photonic materials. However, tuning CT behavior in bowl-shaped chromophores through molecular design and understanding their excited-state dynamics at the single-molecule level remain challenging. Herein, we investigate CT state engineering in bowl-shaped corannulene chromophores equipped with one (C-NMI) or two (C-NBI) annulated naphthalimide units. Pronounced solvatochromic shifts in fluorescence emission and a substantial change in dipole moment, upon photoexcitation, corroborate the enhanced CT character in C-NBI relative to C-NMI at the ensemble level. To probe the influence of local polarity at the single-molecule level, the chromophores were embedded in nonpolar polystyrene (PS) and polar poly(methyl methacrylate) (PMMA) matrices. The resulting fluorescence intensity trajectories (FITs) distinctly resolved locally excited (LE), hybrid LE-CT, and CT emissive states in C-NMI and C-NBI at the single-molecule level. Subsequently, femtosecond transient absorption spectroscopy captured the evolution of LE and CT states together with triplet-state population dynamics in C-NMI and C-NBI, while theoretical investigations further supported the observed triplet-state population behavior. Overall, this work demonstrates the role of molecular architecture and local dielectric environments in dictating excited-state pathways in bowl-shaped corannulene chromophores, opening new avenues for environment-sensitive probes and nanoscale photonic technologies.
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BibTeX
@article{thavamani2026chargetransfer,
title = {{Charge-transfer dynamics in bowl-shaped imide-functionalized corannulenes at ensemble and single-molecule levels}},
author = {Tamizharasan Thavamani and Philip Daniel Maret and Amalnadh T. and Alexander Bausback and Kazutaka Shoyama and Frank Würthner and Mahesh Hariharan},
journal = {Chemical Science},
year = {2026},
month = aug,
doi = {10.1039/d6sc05125a},
url = {https://doi.org/10.1039/d6sc05125a},
note = {CC BY-NC 3.0},
}
RIS
TY - JOUR
TI - Charge-transfer dynamics in bowl-shaped imide-functionalized corannulenes at ensemble and single-molecule levels
AU - Tamizharasan Thavamani
AU - Philip Daniel Maret
AU - Amalnadh T.
AU - Alexander Bausback
AU - Kazutaka Shoyama
AU - Frank Würthner
AU - Mahesh Hariharan
PY - 2026
DA - 2026/08/26
JO - Chemical Science
DO - 10.1039/d6sc05125a
UR - https://doi.org/10.1039/d6sc05125a
AB - Curved aromatic hydrocarbons provide unique platforms for tailoring charge-transfer (CT) excited states for functional optoelectronic and photonic materials. However, tuning CT behavior in bowl-shaped chromophores through molecular design and understanding their excited-state dynamics at the single-molecule level remain challenging. Herein, we investigate CT state engineering in bowl-shaped corannulene chromophores equipped with one (C-NMI) or two (C-NBI) annulated naphthalimide units. Pronounced solvatochromic shifts in fluorescence emission and a substantial change in dipole moment, upon photoexcitation, corroborate the enhanced CT character in C-NBI relative to C-NMI at the ensemble level. To probe the influence of local polarity at the single-molecule level, the chromophores were embedded in nonpolar polystyrene (PS) and polar poly(methyl methacrylate) (PMMA) matrices. The resulting fluorescence intensity trajectories (FITs) distinctly resolved locally excited (LE), hybrid LE-CT, and CT emissive states in C-NMI and C-NBI at the single-molecule level. Subsequently, femtosecond transient absorption spectroscopy captured the evolution of LE and CT states together with triplet-state population dynamics in C-NMI and C-NBI, while theoretical investigations further supported the observed triplet-state population behavior. Overall, this work demonstrates the role of molecular architecture and local dielectric environments in dictating excited-state pathways in bowl-shaped corannulene chromophores, opening new avenues for environment-sensitive probes and nanoscale photonic technologies.
SN - 2041-6520
SN - 2041-6539
ER -