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. 2015 Sep 23;1(6):335-42.
doi: 10.1021/acscentsci.5b00269. Epub 2015 Sep 3.

Synthesis, Properties, and Design Principles of Donor-Acceptor Nanohoops

Evan R Darzi  1 , Elizabeth S Hirst  1 , Christopher D Weber  1 , Lev N Zakharov  1 , Mark C Lonergan  1 , Ramesh Jasti  1
Affiliations

Synthesis, Properties, and Design Principles of Donor-Acceptor Nanohoops

Evan R Darzi et al. ACS Cent Sci. .

Abstract

We have synthesized a series of aza[8]cycloparaphenylenes containing one, two, and three nitrogens to probe the impact of nitrogen doping on optoelectronic properties and solid state packing. Alkylation of these azananohoops afforded the first donor-acceptor nanohoops where the phenylene backbone acts as the donor and the pyridinium units act as the acceptor. The impact on the optoelectronic properties was then studied experimentally and computationally to provide new insight into the effect of functionalization on nanohoops properties.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Wrapping a linear polymer into a cyclic isomer leads to dramatic modulation of the electronic structure. Calculated HOMO–LUMO energy gaps are taken from ref (7).
Figure 2
Figure 2
(a) Nitrogen doped CNT. (b) Azafullerene. (c) Targeted compounds 1 aza[8]CPP, 2 1,15-diaza[8]CPP, 3 1,15,31-triaza[8]CPP, 4N-methylaza[8]CPP triflate, and 5N,N-dimethyl-1,15-diaza[8]CPP ditriflate.
Scheme 1
Scheme 1. Synthesis of [8]CPP and Targets aza[8]CPPs 1–3 and Donor–Acceptor aza[8]CPPs 4 and 5
Figure 3
Figure 3
ORTEP, side-on packing, and top down packing of (a) 1 and (b) 5. (c) Head to tail interaction between one pyridinium acceptor and a neighboring electron-rich phenylene donor in compound 5.
Figure 4
Figure 4
Cyclic Voltammetry of [8]CPP and 1–5.
Figure 5
Figure 5
DFT calculated HOMO and LUMO energy levels and orbital distributions for [8]CPP and nanohoops 1–6.
Figure 6
Figure 6
(a) Scaled (for clarity) UV–vis absorbance (solid lines) and fluorescence (dashed lines) of compounds [8]CPP (blue), aza[8]CPP 1 (green), 1,15-diaza[8]CPP 2 (yellow), and 1,15,31-triaza[8]CPP 3 (red) in dichloromethane. (b) Scaled (for clarity) UV–vis(solid lines) and fluorescence (dashed lines) for compounds [8]CPP (blue), N-methylaza[8]CPP triflate 4 (orange), and N,N-dimethyl-1,15-diaza[8]CPP ditriflate 5 (red) in dichloromethane.
Figure 7
Figure 7
TD-DFT orbital transitions for (a) [8]CPP, (b) 1,15-diaza[8]CPP 2, and (c) N,N-dimethyl-1,15-diaza[8]CPP ditriflate 5. Pictorial orbital transitions for 1, 3, and 4 are found in Supplementary Figure 17. Full orbital transitions for compounds 1–5 are found in Supplementary Tables 1–5.
Figure 8
Figure 8
Theoretical HOMO and LUMO energies for (left) N,N-dimethyl-1,8-diaza[8]CPP, (center) N,N-dimethyl-1,21-diaza[8]CPP, and (right) N,N-dimethyl-1,26-diaza[8]CPP.
Figure 9
Figure 9
Effect of acceptor (red), donor (blue), and donor–acceptor moieties on the HOMO and LUMO energies of [6]CPP and linear [6]OPP frameworks.
See this image and copyright information in PMC

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