Near-Infrared Fluorescence from In-Plane-Aromatic Cycloparaphenylene Dications

The Journal of Physical Chemistry. a
Yui MasumotoMasanobu Uchiyama

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 on 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 relativel...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jan 6, 2005·Journal of the American Chemical Society·Taizoon CanteenwalaLong Y Chiang
Nov 14, 2007·Nano Letters·Lisa J CarlsonTodd D Krauss
Dec 6, 2008·Journal of the American Chemical Society·Ramesh JastiCarolyn R Bertozzi
Feb 12, 2009·ACS Nano·Daniel Sebastiani, Konstantin N Kudin
Jul 10, 2009·Angewandte Chemie·Hiroko TakabaKenichiro Itami
Dec 17, 2009·Angewandte Chemie·Shigeru YamagoTakahiro Iwamoto
Sep 15, 2011·Journal of the American Chemical Society·Thomas J SistoRamesh Jasti
Jan 31, 2012·Angewandte Chemie·Jianlong Xia, Ramesh Jasti
Jul 19, 2012·The Journal of Organic Chemistry·Evan R DarziRamesh Jasti
Sep 28, 2012·Physical Chemistry Chemical Physics : PCCP·Mamoru FujitsukaTetsuro Majima
Nov 21, 2013·Angewandte Chemie·Eiichi KayaharaShigeru Yamago
Jan 28, 2014·Journal of the American Chemical Society·Eiichi KayaharaShigeru Yamago
Dec 20, 2014·Journal of the American Chemical Society·Naoyuki ToriumiMasanobu Uchiyama
Jul 3, 1996·Journal of the American Chemical Society·Paul von Ragué SchleyerNicolaas J R van Eikema Hommes

❮ Previous
Next ❯

Citations

Nov 15, 2018·Physical Chemistry Chemical Physics : PCCP·Mamoru FujitsukaTetsuro Majima
Feb 24, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Rafael LingasAlvaro Muñoz-Castro
Jan 14, 2020·The Journal of Organic Chemistry·Tatsuya KawanishiShigeru Yamago
Jan 12, 2021·The Journal of Physical Chemistry. a·Rabia AyubHenrik Ottosson

❮ Previous
Next ❯

Related Concepts

Related Feeds

Barrel cortex

Here is the latest research on barrel cortex, a region of somatosensory and motor corticies in the brain, which are used by animals that rely on whiskers for world exploration.