skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Theoretical Prediction and Analysis of the UV/Visible Absorption and Emission Spectra of Chiral Carbon Nanorings

Abstract

In this study, UV/vis absorption and emission spectra of recently synthesized chiral carbon nanorings were simulated using first-principles-based molecular dynamics and time-dependent density functional theory (TD-DFT). The chiral carbon nanorings are derivatives of the [n]cycloparaphenylene ([n]CPP) macrocycles, containing an acene unit such as naphthalene, ([n]CPPN), anthracene ([n]CPPA), and tetracene ([n]CPPT), in addition to n paraphenylene units. In order to study the effect of increasing molecular size on absorption and emission spectra, we investigated the cases where n = 6 and 8. Frontier molecular orbital analysis was carried out to give insight into the degree of excitation delocalization and its relationship to the predicted absorption spectra. The lowest excited singlet state S 1 corresponds to a HOMO–LUMO π–π* transition, which is allowed in all chiral carbon nanorings due to lack of molecular symmetry, in contrast to the forbidden HOMO–LUMO transition in the symmetric [n]CPP molecules. The S 1 absorption peak exhibits a blue-shift with increasing number of paraphenylene units in particular for [n]CPPN and [n]CPPA and less so in the case of [n]CPPT. In the case of CPPN and CPPA, the transition density is mainly localized over a semicircle of the macrocycle with the acene unit in its center but ismore » strongly localized on the tetracene unit in the case of CPPT. Molecular dynamics simulations performed on the excited state potential energy surfaces reveal red-shifted emission of these chiral carbon nanorings when the size of the π-conjugated acene units is increased, although the characteristic [n]CPP blue-shift with increasing paraphenylene unit number n remains apparent. Finally, the anomalous emission blue-shift is caused by the excited state bending and torsional motions that stabilize the π HOMO and destabilize the π* LUMO, resulting in an increasing HOMO–LUMO gap.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. King Mongkut’s Institute of Technology Ladkrabang, Bangkok (Thailand). Department of Chemistry, Faculty of Science; Nagoya Univ. (Japan). Institute of Transformative Bio-Molecules (WPI-ITbM) and Department of Chemistry, Graduate School of Science
  2. Nagoya Univ. (Japan). Institute of Transformative Bio-Molecules (WPI-ITbM) and Department of Chemistry, Graduate School of Science; Univ. of Costa Rica, San Jose (Costa Rica). School of Chemistry
  3. Chiang Mai University (Thailand). Department of Chemistry, Faculty of Science and Center of Excellence in Materials Science and Technology
  4. Nagoya Univ. (Japan). Institute of Transformative Bio-Molecules (WPI-ITbM) and Department of Chemistry, Graduate School of Science; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Computational Sciences and Engineering Division and Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1474648
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 37; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Daengngern, Rathawat, Camacho, Cristopher, Kungwang, Nawee, and Irle, Stephan. Theoretical Prediction and Analysis of the UV/Visible Absorption and Emission Spectra of Chiral Carbon Nanorings. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b07270.
Daengngern, Rathawat, Camacho, Cristopher, Kungwang, Nawee, & Irle, Stephan. Theoretical Prediction and Analysis of the UV/Visible Absorption and Emission Spectra of Chiral Carbon Nanorings. United States. doi:10.1021/acs.jpca.8b07270.
Daengngern, Rathawat, Camacho, Cristopher, Kungwang, Nawee, and Irle, Stephan. Thu . "Theoretical Prediction and Analysis of the UV/Visible Absorption and Emission Spectra of Chiral Carbon Nanorings". United States. doi:10.1021/acs.jpca.8b07270. https://www.osti.gov/servlets/purl/1474648.
@article{osti_1474648,
title = {Theoretical Prediction and Analysis of the UV/Visible Absorption and Emission Spectra of Chiral Carbon Nanorings},
author = {Daengngern, Rathawat and Camacho, Cristopher and Kungwang, Nawee and Irle, Stephan},
abstractNote = {In this study, UV/vis absorption and emission spectra of recently synthesized chiral carbon nanorings were simulated using first-principles-based molecular dynamics and time-dependent density functional theory (TD-DFT). The chiral carbon nanorings are derivatives of the [n]cycloparaphenylene ([n]CPP) macrocycles, containing an acene unit such as naphthalene, ([n]CPPN), anthracene ([n]CPPA), and tetracene ([n]CPPT), in addition to n paraphenylene units. In order to study the effect of increasing molecular size on absorption and emission spectra, we investigated the cases where n = 6 and 8. Frontier molecular orbital analysis was carried out to give insight into the degree of excitation delocalization and its relationship to the predicted absorption spectra. The lowest excited singlet state S1 corresponds to a HOMO–LUMO π–π* transition, which is allowed in all chiral carbon nanorings due to lack of molecular symmetry, in contrast to the forbidden HOMO–LUMO transition in the symmetric [n]CPP molecules. The S1 absorption peak exhibits a blue-shift with increasing number of paraphenylene units in particular for [n]CPPN and [n]CPPA and less so in the case of [n]CPPT. In the case of CPPN and CPPA, the transition density is mainly localized over a semicircle of the macrocycle with the acene unit in its center but is strongly localized on the tetracene unit in the case of CPPT. Molecular dynamics simulations performed on the excited state potential energy surfaces reveal red-shifted emission of these chiral carbon nanorings when the size of the π-conjugated acene units is increased, although the characteristic [n]CPP blue-shift with increasing paraphenylene unit number n remains apparent. Finally, the anomalous emission blue-shift is caused by the excited state bending and torsional motions that stabilize the π HOMO and destabilize the π* LUMO, resulting in an increasing HOMO–LUMO gap.},
doi = {10.1021/acs.jpca.8b07270},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 37,
volume = 122,
place = {United States},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share: