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A: Spectroscopy, Molecular Structure, and Quantum Chemistry
Near-Infrared Fluorescence from In-PlaneAromatic Cycloparaphenylene Dications Yui Masumoto, Naoyuki Toriumi, Atsuya Muranaka, Eiichi Kayahara, Shigeru Yamago, and Masanobu Uchiyama J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.8b03105 • Publication Date (Web): 18 May 2018 Downloaded from http://pubs.acs.org on May 18, 2018
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The Journal of Physical Chemistry
Near-Infrared Fluorescence from In-PlaneAromatic Cycloparaphenylene Dications
Yui Masumoto, ,à Naoyuki Toriumi, Atsuya Muranaka,*,‡ Eiichi Kayahara,¤ Shigeru Yamago,*,§ Masanobu Uchiyama*,†,‡
†
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
‡
Elements Chemistry Laboratory, RIKEN Cluster for Pioneering Research (CPR), Wako-shi, Saitama 351-0198, Japan §
Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan
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ABSTRACT
Cycloparaphenylenes (CPPs) are hoop-shaped conjugated hydrocarbons corresponding to partial structures of fullerenes or armchair carbon nanotubes. Here, we examined the fluorescence properties of a series of [n]cycloparaphenylene dications ([n]CPP2+, n = 5-9), which have unique in-plane aromaticity. The fluorescence peak positions of the [n]CPP2+s shifted to the longer-wavelength region with increasing ring size, reaching the near-infrared region for those with n > 5. The fluorescence quantum yield of [6]CPP2+ was the highest among the [n]CPP2+s examined in this study, and the value was of the same order as that of carbon nanotubes. The Stokes shifts of [n]CPP2+s were smaller than those of neutral [n]CPPs, which do not have in-plane aromaticity. Theoretical calculations indicate that [n]CPP2+s undergo smaller structural changes upon S0-S1 transition than [n]CPPs do, and this is responsible for the difference of the Stokes shift. Furthermore, molecular orbital analysis reveals that the S0-S1 transition of smaller [n]CPP2+s has an electric-dipole-forbidden character due to HOMO ! LUMO/HOMO ! LUMO+1 mixing. The relatively high fluorescence quantum yield of [6]CPP2+ is considered to arise from the balance between relatively allowed character and the dominant effect of energy gap.
TEXT Introduction
Nanocarbons having curved surfaces, such as fullerenes and carbon nanotubes, have extraordinary physical and electronic properties, which have led to applications in many areas, including consumer goods, cosmetics, drugs, organic semiconductors, and solar cells.1,2 Cycloparaphenylenes (CPPs), which are hoop-shaped conjugated hydrocarbons consisting of p-substituted benzene, possess a partial structure of fullerenes or armchair carbon nanotubes
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The Journal of Physical Chemistry
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