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. 2023 Jul 31;6(1):159.
doi: 10.1038/s42004-023-00950-1.

Selective emergence of photoluminescence at telecommunication wavelengths from cyclic perfluoroalkylated carbon nanotubes

Yutaka Maeda  1 , Yasuhiro Suzuki  2 , Yui Konno  2 , Pei Zhao  3 , Nobuhiro Kikuchi  2 , Michio Yamada  2 , Masaya Mitsuishi  4 , Anh T N Dao  5   6 , Hitoshi Kasai  5 , Masahiro Ehara  7
Affiliations

Selective emergence of photoluminescence at telecommunication wavelengths from cyclic perfluoroalkylated carbon nanotubes

Yutaka Maeda et al. Commun Chem. .

Abstract

Chemical functionalisation of semiconducting single-walled carbon nanotubes (SWNTs) can tune their local band gaps to induce near-infrared (NIR) photoluminescence (PL). However, tuning the PL to telecommunication wavelengths (>1300 nm) remains challenging. The selective emergence of NIR PL at the longest emission wavelength of 1320 nm was successfully achieved in (6,5) SWNTs via cyclic perfluoroalkylation. Chiral separation of the functionalised SWNTs showed that this functionalisation was also effective in SWNTs with five different chiral angles. The local band gap modulation mechanism was also studied using density functional theory calculations, which suggested the effects of the addenda and addition positions on the emergence of the longest-wavelength PL. These findings increase our understanding of the functionalised SWNT structure and methods for controlling the local band gap, which will contribute to the development and application of NIR light-emitting materials with widely extended emission and excitation wavelengths.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Fig. 1
Fig. 1. Absorption and PL spectra of functionalised SWNT adducts.
a Chemical formulae of the reagents and abbreviations of the corresponding SWNT adducts. b, d Absorption spectra and c, e PL mapping of SWNTs and functionalised SWNTs with increasing numbers of fluorine substituents dispersed in D2O containing 1 wt% SDBS. The peak assignment for (6,5) SWNT (E22 and E11 absorption, E11, E11*, and E11** PL) is shown unless otherwise stated.
Fig. 2
Fig. 2. Separation and assignment of functionalised SWNTs.
HPLC profile of (a) SWNT>(CF2)4 and (b) SWNT-(CF2)3CF3 monitored at 280 nm and gradient proportion of DOC concentration (wt%). Condition: column, ϕ10 × 200 mm; eluent, H2O containing 0.5 wt% SC, 1.0 wt% SDS, and X wt% DOC, where X corresponds to the values shown on the gradient; flow rate, 2 mL min−1. Absorption spectra of separated c SWNT>(CF2)4 and d SWNT-(CF2)3CF3 in D2O containing 1 wt% SC. CD spectra of separated e SWNT>(CF2)4 and f SWNT-(CF2)3CF3 (right) in D2O containing 1 wt% SC normalised by the E22 absorbance.
Fig. 3
Fig. 3. Contour plots of the PL intensity as a function of the excitation and emission wavelengths of the separated SWNT adducts in D2O containing 1 wt% SC.
a SWNT>(CF2)4. b SWNT>(CH2)4. c SWNT-(CF2)3CF3. d CH3(CH2)3-SWNT-H. e SWNT.
Fig. 4
Fig. 4. Emission energy difference (ΔPL) between the functionalised and non-functionalised SWNTs as a function of the SWNT diameter.
SWNT>(CF2)4 (blue, formula image), SWNT>CH2(CF2)2CH2 (purple, formula image), SWNT>(CH2)4 (red, formula image), SWNT-(CF2)3CF3 (green, formula image), and CH3(CH2)3-SWNT-H (black, formula image).
Fig. 5
Fig. 5. Optimised structures, transition energies, and relative energies of SWNT adducts.
Optimised partial structures of a (6,5) SWNT>(CF2)4 and b CF3(CF2)3-(6,5) SWNT-H. c Six binding configurations of (6,5) SWNTs. The binding sites relative to the carbon atoms highlighted in the grey circle are presented as 1,2-L++ (formula image), 1,2-L+ (formula image), 1,2-L- (formula image), 1,4-L++ (formula image), 1,4-L+ (formula image), and 1,4-L- (formula image). d, e Calculated transition energies (eV) and relative energies (kcal/mol) of the model molecules of (6,5) SWNT>(CF2)4, (6,5) SWNT>(CH2)4, CF3(CF2)3-(6,5) SWNT-H, CF3(CF2)2CH2-(6,5) SWNT-H, CF3CF2(CH2)2-(6,5) SWNT-H, and CH3(CH2)3-(6,5) SWNT-H.
See this image and copyright information in PMC

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