Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions

Powell, Lyndsey R.; Piao, Yanmei; Wang, YuHuang

doi:10.1021/acs.jpclett.6b01771

Cited by 46 publications

(91 citation statements)

References 21 publications

(48 reference statements)

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“…It is also important to note that when the binary mixture was protected from light, no defect PL was detected (Figure S13). This indicates that the diazoether chemistry is much more controllable than the light-driven diazonium reaction previously reported by us 20 and oxidation by Star et al 21 …”

Section: Resultsmentioning

confidence: 59%

“…This triggered reactivity is significantly more selective than the widely used diazonium salts either with 20 or without optical excitation, 2 as well as the reactive Z -diazoether. 10 Our experimental results show that without light and H + , the reaction can be completely suppressed at room temperature within the limits of our sensitive spectral technique.…”

Section: Resultsmentioning

confidence: 92%

“…The optical selection technique suggests reaction specificity can be obtained, localized to a certain chirality via the resonant excitation, as discussed in our previous work with diazonium salts. 20 Monitoring the temporal evolution of the defect PL was complicated by the quenching effect of the acid–base reaction products necessary for consecutive PL measurements. For this reason, extensive kinetic studies were not completed, but we do show that defect PL evolves with time in Figure S7 in the case of the photoactivated reaction of (6,5)-SWCNT with the E -isomer of the diazoether at pH 3.69.…”

Section: Resultsmentioning

confidence: 99%

“…3- O - p -Nitrobenzenediazoascorbic acid was isolated using a modified procedure from Doyle et al 22 First p -nitrobenzenediazonium tetrafluoroborate was synthesized as we previously described 20 from p -nitroaniline (99%, Sigma-Aldrich) and nitrous acid (48 wt% tetrafluoroboric acid solution in water, Sigma-Aldrich; sodium nitrite, 97%, Sigma-Aldrich). The diazonium salt was coupled to L-ascorbic acid (99%, Sigma-Aldrich) at room temperature, the solvent was removed, and the yellow solid precipitate was dried and recrystallized from 2-butanone (99%, Sigma-Aldrich) with dichloromethane (99.5%, Sigma-Aldrich) at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…18,19 This allows the defect PL to be used as a sensitive quantitative indicator of functional degree that can be used to monitor the surface chemistry of SWCNTs in situ . 20 …”

Section: Introductionmentioning

confidence: 99%

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Chirality-Selective Functionalization of Semiconducting Carbon Nanotubes with a Reactivity-Switchable Molecule

2017

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Chirality-selective functionalization of semiconducting single-walled carbon nanotubes (SWCNTs) has been a difficult synthetic goal for more than a decade. Here we describe an on-demand covalent chemistry to address this intriguing challenge. Our approach involves the synthesis and isolation of a chemically inert diazoether isomer that can be switched to its reactive form in situ by modulation of the thermodynamic barrier to isomerization with pH and visible light that resonates with the optical frequency of the nanotube. We found that it is possible to completely inhibit the reaction in the absence of light, as determined by the limit of sensitive defect photoluminescence (less than 0.01% of the carbon atoms are bonded to a functional group). This optically driven diazoether chemistry makes it possible to selectively functionalize a specific SWCNT chirality within a mixture. Even for two chiralities that are nearly identical in diameter and electronic structure, (6,5)- and (7,3)-SWCNTs, we are able to activate the diazoether compound to functionalize the less reactive (7,3)-SWCNTs, driving the chemical reaction to near exclusion of the (6,5)-SWCNTs. This work opens opportunities to chemically tailor SWCNTs at the single chirality level for nanotube sorting, on-chip passivation, and nanoscale lithography.

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Section: Resultsmentioning

confidence: 59%

Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…18,19 This allows the defect PL to be used as a sensitive quantitative indicator of functional degree that can be used to monitor the surface chemistry of SWCNTs in situ . 20 …”

Section: Introductionmentioning

confidence: 99%

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Chirality-Selective Functionalization of Semiconducting Carbon Nanotubes with a Reactivity-Switchable Molecule

2017

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Photolithographic Patterning of Organic Color‐Centers

Huang

Powell

et al. 2020

Advanced Materials

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Organic color‐centers (OCCs) have emerged as promising single‐photon emitters for solid‐state quantum technologies, chemically specific sensing, and near‐infrared bioimaging. However, these quantum light sources are currently synthesized in bulk solution, lacking the spatial control required for on‐chip integration. The ability to pattern OCCs on solid substrates with high spatial precision and molecularly defined structure is essential to interface electronics and advance their quantum applications. Herein, a lithographic generation of OCCs on solid‐state semiconducting single‐walled carbon nanotube films at spatially defined locations is presented. By using light‐driven diazoether chemistry, it is possible to directly pattern p‐nitroaryl OCCs, which demonstrate chemically specific spectral signatures at programmed positions as confirmed by Raman mapping and hyperspectral photoluminescence imaging. This light‐driven technique enables the fabrication of OCC arrays on solid films that fluoresce in the shortwave infrared and presents an important step toward the direct writing of quantum emitters and other functionalities at the molecular level.

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Luminescent Defects in Single‐Walled Carbon Nanotubes for Applications

Zaumseil

2021

Advanced Optical Materials

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most applications, only semiconducting nanotubes and ideally only one (n,m) species (monochiral) are desired. This technological need has pushed the search for more controlled and selective growth of SWCNTs [5,6] and even more importantly fueled the development of post-growth purification and sorting of the different nanotube types and chiralities. Various, quite different techniques, such as gelchromatography, [7][8][9] aqueous two-phase separation (ATPE), [10][11][12] and selective polymer-wrapping, [13][14][15][16][17] now make it possible to produce and work with sufficiently large amounts of not only purely semiconducting nanotubes of a certain diameter range but also monochiral nanotubes and even enantiomerically pure samples. [18,19] This high degree of purification and hence the availability of nanotubes as a material with reproducible properties has been critical for applications in electronics [20,21] and energy conversion, [22,23] as well as imaging [24,25] and sensing [26,27] based on the near-infrared photoluminescence (PL) of SWCNTs and its modulation. However, an important paradigm shift occurred when it became clear that defects in the sp 2 carbon lattice of nanotubes are not always detrimental to the photoluminescence yield, but can indeed lead to new electronic states with highly interesting and useful optical properties. [28][29][30] These specific defects, which are variably named sp 3 defects, luminescent defects, organic color centers or quantum defects [31][32][33][34][35] have been at the heart of many recent studies on carbon nanotubes and promise a wide range of potential applications from single-photon emission to in vivo super-resolution imaging. This review will briefly introduce the underlying photo physics and properties of these defects, peruse recent progress in their controlled creation and discuss the various potential applications in detail.Semiconducting single-walled carbon nanotubes show extraordinary electronic and optical properties, such as high charge carrier mobilities and diameter-dependent near-infrared photoluminescence. The introduction of sp 3 defects in the carbon lattice of these nanotubes creates new electronic states that result in even further red-shifted photoluminescence with longer lifetimes and higher photoluminescence yield. These luminescent defects or organic color centers can be tuned chemically by controlling the precise binding configuration and the electrostatic properties of the attached substituents. This review covers the basic photophysics of luminescent sp 3 defects, synthetic methods for their controlled formation and discusses their application as near-infrared single-photon emitters at room temperature, in electroluminescent devices, as versatile optical sensors, and as fluorophores for bioimaging and potential super-resolution microscopy.

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Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions

Cited by 46 publications

References 21 publications

Chirality-Selective Functionalization of Semiconducting Carbon Nanotubes with a Reactivity-Switchable Molecule

Chirality-Selective Functionalization of Semiconducting Carbon Nanotubes with a Reactivity-Switchable Molecule

Photolithographic Patterning of Organic Color‐Centers

Luminescent Defects in Single‐Walled Carbon Nanotubes for Applications

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