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 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 localizedmore » 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:

Daengngern, Rathawat  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-4425-3969"

Camacho, Cristopher ^[2]; Kungwang, Nawee  ^[3];

• Search DOE PAGES for author "Kungwang, Nawee"
• Search DOE PAGES for ORCID "0000-0002-2960-6853"

Irle, Stephan  ^[4]

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• Search DOE PAGES for ORCID "0000-0003-4995-4991"

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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:

Thu Aug 30 00:00:00 EDT 2018

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