Molecular Encapsulation of Naphthalene Diimide (NDI) Based π‐Conjugated Polymers: A Tool for Understanding Photoluminescence

Royakkers, Jeroen; Guo, Kunping; Toolan, Daniel T. W.; Feng, Liang‐Wen; Minotto, Alessandro; Congrave, Daniel G.; Danowska, Magda; Zeng, Weixuan; Bond, Andrew D.; Al‐Hashimi, Mohammed; Marks, Tobin J.; Facchetti, Antonio; Cacialli, Franco; Bronstein, Hugo

doi:10.1002/ange.202110139

Cited by 5 publications

(4 citation statements)

References 73 publications

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“…First, the amine end-capped side chain containing six EG repeating units was prepared from 2, 5, 8, 11, 14, 17-hexaoxanonadecan-19-ol within three steps in a total yield of 72%. [42] Then, 1, 4, 5, 8-naphthalenetetracarboxylic dianhydride was treated in turn with 1, 3-dibromo-5, 5-dimethylhydantoin in sulfuric acid, [43] followed by an excess of the synthesized amine end-capped EG side chain to yield the target NDI monomer for polymerization. [44] Besides, the stannylated EDOT and BT were synthesized as previous literatures [45,46] while the stannylated FBT was commercially available.…”

Section: Synthesis Of the Ndi Copolymersmentioning

confidence: 99%

Donor Functionalization Tuning the N‐Type Performance of Donor–Acceptor Copolymers for Aqueous‐Based Electrochemical Devices

Cong

Chen

Wang

et al. 2022

Adv Funct Materials

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In this work, three n‐type donor–acceptor copolymers consisting of glycolated naphthalene tetracarboxylicdiimide (gNDI) coupled with variable donating companion moieties are reported. Using 2,2′‐bis(3,4‐ethylenedioxy)bithiophene, 2,2′‐bithiophene, 3,3′‐difluoro‐2,2′‐bithiophene (FBT), the donating strength of the donor units is systematically functionalized. These copolymers are used as a platform for aqueous‐based electrochemical devices, including energy‐storage devices, electrochromic devices (ECDs), and organic electrochemical transistors (OECTs). It is found that the electrochemical redox stability and electron mobility of copolymers are significantly improved via weakening the electron‐donating strength of donor units. gNDI coupling with FBT (gNDI‐FBT) exhibits a charge‐storage capacity exceeding 190 Fg−1, which is the highest value reported to date for NDI‐based polymer electrodes in aqueous media. For ECDs, gNDI‐FBT remains 100% of initial electrochromism contrast (∆%T = 20%) up to 1200 s. In addition, gNDI‐FBT outperforms its two analogs in OECTs, including lower threshold voltage (0.19 V), faster response time (45.5 ms), and higher volumetric capacitance (197 F cm−3). Moreover, gNDI‐FBT with fluorine atoms leads to the bipolarons delocalization along the polymer backbone and favorable molecular packing for ion–electron transport. Through such weak donor functionalization strategy, this work provides ways for n‐type copolymers tuning to access desirable performance metrics in optical, electrochemical, and bioelectronic applications.

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Section: Synthesis Of the Ndi Copolymersmentioning

confidence: 99%

Donor Functionalization Tuning the N‐Type Performance of Donor–Acceptor Copolymers for Aqueous‐Based Electrochemical Devices

Cong

Chen

Wang

et al. 2022

Adv Funct Materials

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“…This result mainly originates from the decreased fraction of π‐conjugated bonds in the polymer backbone enhancing backbone conformational freedom. [ 18 ]…”

Section: Resultsmentioning

confidence: 99%

“…[ 1–12 ] Effective FOTFT fabrication relies on several strategies, such as positioning the entire device, and particularly the most mechanically sensitive components, in the neutral plane of a multilayer architecture to alleviate mechanical stress on bending. [ 13–21 ] Another FOTFT design strategy utilizes polymeric material components with greater tolerance to mechanical stresses. [ 22–29 ] Thus, Bao et al.…”

Section: Introductionmentioning

confidence: 99%

Mechanical, Morphological, and Charge Transport Properties of NDI Polymers with Variable Built‐in Π‐Conjugation Lengths Probed by Simulation and Experiment

Zhao,

Kim,

Ghosh

et al. 2023

Adv Funct Materials

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Mechanically deformable polymeric semiconductors are a key material for fabricating flexible organic thin‐film transistors (FOTFTs)—the building block of electronic circuits and wearable electronic devices. However, for many π‐conjugated polymers achieving mechanical deformability and efficient charge transport remains challenging. Here the effects of polymer backbone bending stiffness and film microstructure on mechanical flexibility and charge transport are investigated via experimental and computational methods for a series of electron‐transporting naphthalene diimide (NDI) polymers having differing extents of π‐conjugation. The results show that replacing increasing amounts of the π‐conjugated comonomer dithienylvinylene (TVT) with the π‐nonconjugated comonomer dithienylethane (TET) in the backbone of the fully π‐conjugated polymeric semiconductor, PNDI‐TVT100 (yielding polymeric series PNDI‐TVTx, 100 ≥ x ≥ 0), lowers backbone rigidity, degree of texturing, and π–π stacking interactions between NDI moieties. Importantly, this comonomer substitution increases the mechanical robustness of PNDI‐TVTx while retaining efficient charge transport. Thus, reducing the TVT content of PNDI‐TVTx suppresses film crack formation and dramatically stabilizes the field‐effect electron mobility upon bending (e.g., 2 mm over 2000 bending cycles). This work provides a route to tune π–π stacking in π‐conjugated polymers while simultaneously promoting mechanical flexibility and retaining good carrier mobility in FOTFTs.

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“…[7,[38][39][40] Also shown in Scheme 1 is the specific focus of this current report; that is, a new class of doubly strapped and conjugatable NIR-I and NIR-II heptamethine cyanine dyes with greatly enhanced performance properties. The literature on doubly strapped dyes includes several organicsoluble examples [41][42][43][44][45][46] and one water-soluble molecule. [47] Most do not emit in the NIR region and none have been designed for bioconjugation in water.…”

Section: Introductionmentioning

confidence: 99%

Doubly Strapped Zwitterionic NIR‐I and NIR‐II Heptamethine Cyanine Dyes for Bioconjugation and Fluorescence Imaging

Gamage

Oliver

et al. 2023

Angewandte Chemie

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Heptamethine cyanine dyes enable deep tissue fluorescence imaging in the near infrared (NIR) window. Small molecule conjugates of the benchmark dye ZW800‐1 have been tested in humans. However, long‐term imaging protocols using ZW800‐1 conjugates are limited by their instability, primarily because the chemically labile C4′‐O‐aryl linker is susceptible to cleavage by biological nucleophiles. Here, we report a modular synthetic method that produces novel doubly strapped zwitterionic heptamethine cyanine dyes, including a structural analogue of ZW800‐1, with greatly enhanced dye stability. NIR‐I and NIR‐II versions of these doubly strapped dyes can be conjugated to proteins, including monoclonal antibodies, without causing undesired fluorophore degradation or dye stacking on the protein surface. The fluorescent antibody conjugates show excellent tumor‐targeting specificity in a xenograft mouse tumor model. The enhanced stability provided by doubly strapped molecular design will enable new classes of in vivo NIR fluorescence imaging experiments with possible translation to humans.

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Molecular Encapsulation of Naphthalene Diimide (NDI) Based π‐Conjugated Polymers: A Tool for Understanding Photoluminescence

Cited by 5 publications

References 73 publications

Donor Functionalization Tuning the N‐Type Performance of Donor–Acceptor Copolymers for Aqueous‐Based Electrochemical Devices

Donor Functionalization Tuning the N‐Type Performance of Donor–Acceptor Copolymers for Aqueous‐Based Electrochemical Devices

Mechanical, Morphological, and Charge Transport Properties of NDI Polymers with Variable Built‐in Π‐Conjugation Lengths Probed by Simulation and Experiment

Doubly Strapped Zwitterionic NIR‐I and NIR‐II Heptamethine Cyanine Dyes for Bioconjugation and Fluorescence Imaging

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