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, 141 (10), 4230-4234

Regioselective Hydrogenation of a 60-Carbon Nanographene Molecule Toward a Circumbiphenyl Core

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Regioselective Hydrogenation of a 60-Carbon Nanographene Molecule Toward a Circumbiphenyl Core

Xuelin Yao et al. J Am Chem Soc.

Abstract

Regioselective peripheral hydrogenation of a nanographene molecule with 60 contiguous sp2 carbons provides unprecedented access to peralkylated circumbiphenyl (1). Conversion to the circumbiphenyl core structure was unambiguously validated by MALDI-TOF mass spectrometry, NMR, FT-IR, and Raman spectroscopy. UV-vis absorption spectra and DFT calculations demonstrated the significant change of the optoelectronic properties upon peripheral hydrogenation. Stimulated emission from 1, observed via ultrafast transient absorption measurements, indicates potential as an optical gain material.

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
“π-Expansion” toward circumbiphenyl 2 by E. Clar and the postsynthetic “π-truncation” to peralkylated circumbiphenyl 1.
Figure 2
Figure 2
High-resolution MALDI-TOF MS spectrum of 1 and 4 (inset: the corresponding experimental and simulated isotopic distributions of 1).
Figure 3
Figure 3
Representative FTIR spectra regions of 1 (blue line) and 4 (red line) measured on powder samples.
Figure 4
Figure 4
(a) Normalized UV–vis absorption and fluorescence spectra (excited at the absorption maxima) of 1 and 4 in THF solution (2 × 10–5 M) (inset: emission of 1 and 4 under 365 nm wavelength of UV lamp). (b) Frontier molecular orbitals and energy diagrams of 1, 2 and 4 at the B3LYP/6-311G(d) level. For simplicity of computation, dodecyl chains of 1 and 4 were removed.
Figure 5
Figure 5
(a) Femtosecond transient absorption spectra of 1 and 4 in THF solution at 1 fs pump–probe delay obtained by exciting at 470 nm and probing with a broadband probe light. (b) Transient dynamics for 1 and 4 at a probe wavelength of 500 nm. The solid blue and red lines represent the biexponential best-fit curves for 1 and 4, respectively.

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