Reconfiguration of π-conjugated superstructures enabled by redox-assisted assembly

Liu, Kaixuan; Mukhopadhyay, Arindam; Ashcraft, A. C.; Liu, Chuan; Levy, Adam S.; Blackwelder, Patricia; Olivier, J.

doi:10.1039/c9cc01939a

Cited by 14 publications

(26 citation statements)

References 28 publications

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“…In addition, the emergence of a broad NIR band that spans from 900 to 2500 nm observed in Figure S5 diagnoses the formation of π-anion stacks as reported by us and others. 63,66,69,70 Further excursion toward the cathodic potentials (−0.7 V to −1.0 V vs Ag/AgCl) initiates the apparition of spectroscopic features reminiscent to those of the NDI dianion species as chronicled in Figures S4 and S5.…”

Section: ■ Results and Discussionmentioning

confidence: 90%

Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces

Mukhopadhyay

Paulino

Liu

et al. 2021

ACS Appl. Mater. Interfaces

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The functionalization of silicon electrodes with π-conjugated chromophores opens new avenues to engineer hybrid semiconducting interfaces relevant to information storage and processing. Notably, molecularly dissolved π-conjugated units, such as ferrocene derivatives, are traditionally exploited as building blocks to construct well-defined interfaces that establish electrochemically addressable platforms with which to investigate electron transfer properties and charge storage capabilities. In contrast, planar π-conjugated building blocks such as naphthalene diimide (NDI) cores enable the formation of solvated aggregates equipped with emergent electronic structures not manifested by the parent, molecularly dissolved building blocks. To interrogate the extent to which the aggregated states of π-conjugated chromophores can be leveraged to regulate the n-type semiconducting properties of functionalized electrodes, we have devised an amphiphilic rylene core (NDI) that demonstrates a non-negligible degree of aggregation in an aqueous medium. Characterization of the electronic structures of the NDI-derived aggregates using a combination of electrochemistry, reductive titration experiments, and spectroelectrochemistry unveils the existence of π-anion stacks, the formation of which is contingent on the initial concentration of NDI building blocks. We show that grafting n-doped NDI aggregates on silicon electrode precursors equipped with a high density of anchoring groups by means of “click” reaction enables the formation of the hybrid Si-NDI electrode (Si-NDI-15@1) that facilitates electron injection by more than 400 mV when compared to Si interfaces constructed from molecularly dissolved NDI units. Furthermore, the engineering of a Si precursor surface characterized by a low density of anchoring groups provides additional proof to highlight that the potentiometric properties recorded for Si-NDI-15@1 originate from NDI units, evidencing a non-negligible degree of aggregation. The present work delivers tools to manipulate the potentiometric properties of functionalized electrodes by leveraging on the electronic structures of aggregated, π-conjugated precursors.

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Section: ■ Results and Discussionmentioning

confidence: 90%

Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces

Mukhopadhyay

Paulino

Liu

et al. 2021

ACS Appl. Mater. Interfaces

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“…To quantify the degree of electronic interaction between NDI units, the excitonic coupling J 12 was calculated by exploiting the model developed by Spano and used by us, and others, on rylene-derived aggregates. ,,− Figure C reports the J 12 values calculated for the (NDI-Triazo) 5 and (NDI-Am) 5 oligomers as a function of the oligomer concentration. While the excitonic coupling among NDI units in (NDI-Triazo) 5 is modestly higher than that calculated for the (NDI-Am) 5 oligomers, it is interesting to note that the J 12 values for both oligomers vary only marginally across the concentration range probed (5–100 μM).…”

Section: Resultsmentioning

confidence: 99%

Molecular Engineering of Water-Soluble Oligomers to Elucidate Radical π–Anion Interactions in n-Doped Nanoscale Objects

et al. 2021

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Modulating, by design, the electronic properties of nanoscale objects that are water-compatible is at the forefront to develop redox-responsive materials capable of interfacing and probing living organisms. In the present work, we report the synthesis and structural and electronic characterizations of two novel water-soluble naphthalene diimide (NDI) oligomers that differ in the nature of the flexible chemical linkages tethering the πconjugated cores. Ground-state electronic absorption spectroscopy experiments, performed as a function of oligomer concentration in an aqueous medium, reveal negligible interactions between oligomer chains but significant interactions among NDI units that comprise a single oligomer chain. Contrasting the monomer controls, which demonstrate well-resolved first and second reduction processes, the NDI oligomers exhibit complex redox processes suggesting the screening of injected charges in the oligomer chains. We show that the flexible chemical linkages offer a synthetic handle to stabilize the first reduction potentials by more than 325 mV when compared to monomer controls. Because the electronic structures of these water-soluble oligomers are characterized by low-lying reduction potentials (E 0/-= −0.025 V vs SCE), biologically relevant sacrificial electron donors, sodium ascorbate and sodium hydrosulfide, possess sufficient driving force to incrementally n-dope the NDI oligomers. Further supported by spectroelectrochemical measurements and time-dependent density functional theory (TD-DFT) calculations, the spectroscopic properties of the reduced NDI units indicate the emergence of novel spectroscopic states diagnostic of radical π−anion interactions. The existence of delocalized electron spin density is unraveled by electron paramagnetic resonance spectroscopy and is shown to be dependent on the strength of the sacrificial electron donors used to n-dope the NDI oligomer chains. Our results not only deliver new insights into the spectroscopic signatures that allow for tracking π−anion interactions in NDI-derived superstructures but also provide new avenues to tune electron spin properties in water-soluble nanoscale objects.

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“…For the synthesis of P (N,N′-Bis(Ethyl-diethoxyethyl-ethylamine)perylene-3,4,9,10-bis(dicarboximide), 200 μL of 2,2-(Ethylenedioxy)bis(ethylamine) (1 mmol) were mixed in 10 mL ethylene glycol in a 100 mL Erlenmeyer flask [ 37 , 38 ]. Afterwards, 20 mg (0.05 mmol) of perylene-3,4,10-tetra-carbocyl dianhydride (PDA) were added to the previous, and the mixture was sonicated for 1 min.…”

Section: Methodsmentioning

confidence: 99%

A Selective Ratiometric Fluorescent Probe for No-Wash Detection of PVC Microplastic

et al. 2021

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Microplastics (MP) are micrometric plastic particles present in drinking water, food and the environment that constitute an emerging pollutant and pose a menace to human health. Novel methods for the fast detection of these new contaminants are needed. Fluorescence-based detection exploits the use of specific probes to label the MP particles. This method can be environmentally friendly, low-cost, easily scalable but also very sensitive and specific. Here, we present the synthesis and application of a new probe based on perylene-diimide (PDI), which can be prepared in a few minutes by a one-pot reaction using a conventional microwave oven and can be used for the direct detection of MP in water without any further treatment of the sample. The green fluorescence is strongly quenched in water at neutral pH because of the formation dimers. The ability of the probe to label MP was tested for polyvinyl chloride (PVC), polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polystyrene (PS), poly methyl methacrylate (PMMA) and polytetrafluoroethylene (PTFE). The probe showed considerable selectivity to PVC MP, which presented an intense red emission after staining. Interestingly, the fluorescence of the MP after labeling could be detected, under excitation with a blue diode, with a conventional CMOS color camera. Good selectivity was achieved analyzing the red to green fluorescence intensity ratio. UV–Vis absorption, steady-state and time-resolved fluorescence spectroscopy, fluorescence anisotropy, fluorescence wide-field and confocal laser scanning microscopy allowed elucidating the mechanism of the staining in detail.

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Reconfiguration of π-conjugated superstructures enabled by redox-assisted assembly

Abstract: Redox-assisted assembly enforces reconfiguration of π-conjugated superstructures.

Cited by 14 publications

References 28 publications

Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces

Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces

Molecular Engineering of Water-Soluble Oligomers to Elucidate Radical π–Anion Interactions in n-Doped Nanoscale Objects

A Selective Ratiometric Fluorescent Probe for No-Wash Detection of PVC Microplastic

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