Blending the Optical and Redox Properties of Oligoynes and Boron Difluoride Formazanates

Dhindsa, Jasveer S.; Cotterrill, Erin L; Buguis, Francis L.; Anghel, Michael; Boyle, Paul D.; Gilroy, Joe B.

doi:10.1002/anie.202208502

Cited by 9 publications

(11 citation statements)

References 74 publications

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“…36 The BF[n]Si polyynes are stable in solution and as solids for several weeks. 34 The yields drop substantially for both PtF…”

Section: Oxidative Acetylenic Coupling Reactionsmentioning

confidence: 97%

“…A combination of the BF 2 -formazanate end group with a polyyne backbone gives BF[n] unique panchromatic absorption and tunable redox properties. 34 The synthesis of RuRu[n] relies on in situ desilylation of the corresponding SiEt 3 -protected polyynes followed by the Hay reaction, and the stable polyyne products are purified by column chromatography. 35 Extensive voltammetric and spectroelectrochemical studies, combined with DFT calculations, outlined electronic coupling across the sp-carbon bridges.…”

Section: Oxidative Acetylenic Coupling Reactionsmentioning

confidence: 99%

“…Gilroy and co-workers show that polyynes end-capped with BF 2 -formazanate dyes, BF[ n ] , are formed using the Hay reaction. A combination of the BF 2 -formazanate end group with a polyyne backbone gives BF[ n ] unique panchromatic absorption and tunable redox properties …”

Section: General Synthetic Strategies For Polyynesmentioning

confidence: 99%

“…Starting with BF[6]Si , a sequence of desilylation and the Hay reaction with H–[CC] 2 –Si i Pr 3 (10 equiv) is used to effect chain elongation for polyynes BF[ n ]Si (Scheme b). The BF[ n ]Si polyynes are stable in solution and as solids for several weeks …”

Section: General Synthetic Strategies For Polyynesmentioning

confidence: 99%

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Advances in Polyynes to Model Carbyne

Gao

Tykwinski

2022

Acc. Chem. Res.

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Conspectus The formation and study of molecules that model the sp-hybridized carbon allotrope, carbyne, is a challenging field of synthetic physical organic chemistry. The target molecules, oligo- and polyynes, are often the preferred candidates as models for carbyne because they can be formed with monodisperse lengths as well as defined structures. Despite a simple linear structure, the synthesis of polyynes is often far from straightforward, due in large part to a highly conjugated framework that can render both precursors and products highly reactive, i.e., kinetically unstable. The vast majority of polyynes are formed as symmetrical products from terminal alkynes as precursors via an oxidative, acetylenic homocoupling reaction based on the Glaser, Eglinton–Galbraith, and Hay reactions. These reactions are very efficient for the synthesis of shorter polyynes (e.g., hexaynes and octaynes), but yields often drop dramatically as a function of length for longer derivatives, usually starting with the formation of decaynes. The most effective approach to circumvent unstable precursors and products has been through the incorporation of sterically demanding end groups that serve to “protect” the polyyne skeleton. This approach was arguably identified in the early 1950s by Bohlmann and co-workers with the synthesis of tBu-end-capped polyynes. During the next 50 years, a polyyne with 14 contiguous alkyne units remained the longest isolated derivative until 2010, when the record was extended to 22 alkyne units. The record length was broken again in 2020, when a polyyne consisting of 24 alkynes was isolated and characterized. Beyond polyynes, there have been several reports describing the potential synthesis of carbyne, but conclusive characterization and proof of structure have been tenuous. The sole example of synthetic carbyne arises from synthesis within carbon nanotubes, when chains of thousands of sp carbon atoms have been linked to form polydisperse samples of carbyne. Thus, model compounds for carbyne, the polyynes, remain the best means to examine and predict the experimental structure and properties of this carbon allotrope. This Account will discuss the general synthesis of polyynes using homologous series of polyynes with up to 10 alkyne units as examples (decaynes). The limited number of specific syntheses of series with longer polyynes will then be presented and discussed in more detail based on end groups. The monodisperse polyynes produced from these synthetic efforts are then examined toward providing our best extrapolations for the expected characteristics for carbyne based on 13C NMR spectroscopy, UV–vis spectroscopy, X-ray crystallography, and Raman spectroscopy.

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“…36 The BF[n]Si polyynes are stable in solution and as solids for several weeks. 34 The yields drop substantially for both PtF…”

Section: Oxidative Acetylenic Coupling Reactionsmentioning

confidence: 97%

Section: Oxidative Acetylenic Coupling Reactionsmentioning

confidence: 99%

Section: General Synthetic Strategies For Polyynesmentioning

confidence: 99%

Section: General Synthetic Strategies For Polyynesmentioning

confidence: 99%

See 2 more Smart Citations

Advances in Polyynes to Model Carbyne

Gao

Tykwinski

2022

Acc. Chem. Res.

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“…This molecule was used for targeted imaging of cancer cells and monitoring of receptor-mediated endocytosis process due to the strong red emission and high photostability. Gallium porphyrins used as end groups for polyynes up to triyne were reported by Tykwinski, while polyynes with chain length up to octatetrayne were used to bridge boron subphtalocyanines by Nielsen. , Very recently, Gilroy and co-workers reported the synthesis of polyynes capped with boron difluoride formazanates end groups exhibiting panchromatic absorption and multiple and tunable reversible redox waves …”

Section: Introductionmentioning

confidence: 99%

Hybrids of Polyynes and Azo Dyes: Synthesis, Characterization, and Two-Photon Absorption

Kruszewska-Bąk,

Deska,

Matczyszyn

et al. 2023

J. Phys. Chem. C

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Polyynes are one-dimensional carbon atomic wires possessing sp hybridization and alternating triple and single bonds. Their electronic structure is particularly attractive and has a significant impact on their optical properties. Here, we report the first synthesis and characterization of blends of polyynes and azo dyes. The dominant contribution of the azo tautomer in the resulting dye end-capped linear carbon rods was unambiguously confirmed using X-ray single-crystal diffraction. Linear and non-linear optical properties of the hybrids of polyynes and azo dyes were investigated in detail and influence of the length of sp-hybridized carbon chain on two-photon absorption (2PA) was analyzed. Reported RC 8 R hybrids of azo dye and polyyne moieties exhibit significantly stronger two-photon absorption compared to the previously reported aryl-substituted polyynes or parent alkyne-substituted azo dye RC 2 TMS.

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Dyads and Triads of Boron Difluoride Formazanate and Boron Difluoride Dipyrromethene Dyes

Buguis,

Hsu,

Sirohey

et al. 2023

Chemistry A European J

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Dye‐dye conjugates have attracted significant interest for their utility in applications such as bioimaging, theranostics, and light‐harvesting. Many classes of organic dyes have been employed in this regard; however, building blocks don’t typically extend beyond small chromophores. This can lead to minor changes to the optoelectronic properties of the original dye. The exploration of dye–dye structures is impeded by long synthetic routes, incompatible synthetic conditions, or a mismatch of the desired properties. Here, we present the first‐of‐their‐kind dye‐dye conjugates of boron difluoride complexes of formazanate and dipyrromethene ligands. These conjugates exhibit dual photoluminescence bands that reach the near‐infrared spectral region and implicate anti‐Kasha processes. Cyclic voltammetry experiments revealed the generation of polyanionic species that can reversibly tolerate the uptake of up to 6 electrons. Ultimately, we demonstrate that BF2 formazanates can serve as a synthetically accessible platform to build upon new classes of dye‐dye conjugates.

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Blending the Optical and Redox Properties of Oligoynes and Boron Difluoride Formazanates

Cited by 9 publications

References 74 publications

Advances in Polyynes to Model Carbyne

Advances in Polyynes to Model Carbyne

Hybrids of Polyynes and Azo Dyes: Synthesis, Characterization, and Two-Photon Absorption

Dyads and Triads of Boron Difluoride Formazanate and Boron Difluoride Dipyrromethene Dyes

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