Dithienophosphole‐Based Phosphinamides with Intriguing Self‐Assembly Behavior

Wang, Zisu; Gelfand, Benjamin S.; Baumgartner, Thomas

doi:10.1002/anie.201511171

Cited by 37 publications

(29 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Within the framework of the given general methodology,e xtensive studies were devotedt ot he family of dyesb ased on the five-membered phospholes. [5] The prominentf eature of these heterocycles, especially those containingapentavalent P atom, is ap henomenon of hyperconjugation. Such s*(exo-P-C)p*i nteraction markedly stabilizes the LUMO level and ensures the tunability of their electron-accepting properties.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Phosphacyclization: Polyaromatic Phosphonium P‐Heterocycles with Wide‐Tuning Optical Properties

Belyaev

Chen

Liu

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

Rationally designed cationic phospha‐polyaromatic fluorophores were prepared through intramolecular cyclization of the tertiary ortho ‐(acene)phenylene‐phosphines mediated by Cu II triflate. As a result of phosphorus quaternization, heterocyclic phosphonium salts 1 c – 3 c , derived from naphthalene, phenanthrene, and anthracene cores, exhibited very intense blue to green fluorescence ( Φ em =0.38–0.99) and high photostability in aqueous medium. The structure–emission relationship was further investigated by tailoring the electron‐donating functions to the anthracene moiety to give dyes 4 c – 6 c with charge‐transfer character. The latter significantly decreases the emission energy to reach near‐IR region. Thus, the intramolecular phosphacyclization renders an ultra‐wide tuning of fluorescence from 420 nm ( 1 c ) to 780 nm ( 6 c ) in solution, extended to 825 nm for 6 c in the solid state with quantum efficiency of approximately 0.07. The physical behavior of these new dyes was studied spectroscopically, crystallographically, and electrochemically, whereas computational analysis was used to correlate the experimental data with molecular electronic structures. The excellent stability, water solubility, and attractive photophysical characteristics make these phosphonium heterocycles powerful tools in cell imaging.

show abstract

Section: Introductionmentioning

confidence: 99%

Intramolecular Phosphacyclization: Polyaromatic Phosphonium P‐Heterocycles with Wide‐Tuning Optical Properties

Belyaev

Chen

Liu

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Phosphorus as the heteroatom would be particularly appealingi ns uch systems as it provides for additional chemistry to adjust the structural, photophysical, and redox properties. [11] It is thus all the more surprising that there is hardlya nything known aboutt he combination of p-conjugated polycyclic scaffoldsi ncorporating phosphorus with the dicyanomethylene acceptors. [12] Here, we introduce an ew family of stable electron acceptors comprising an acridophosphine scaffold with ab ridging dicyanomethylenem oiety that are prone to reversible two-electron reduction under electrochemical conditions.…”

mentioning

confidence: 99%

Organic Electron Acceptors Comprising a Dicyanomethylene‐Bridged Acridophosphine Scaffold: The Impact of the Heteroatom

Schaub

Brülls

Dral

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

Stable two-electron acceptors comprising a dicyanomethylene-bridged acridophosphine scaffold were synthesized and their reversible reduction potentials were efficiently tuned through derivatization of the phosphorus center. X-ray crystallographic analysis combined with NMR, UV/Vis, IR spectroscopic, and electrochemical studies, supported by theoretical calculations, revealed the crucial role of the phosphorus atom for the unique redox, structural, and photophysical properties of these compounds. The results identify the potential of these electron deficient scaffolds for the development of functional n-type materials and redox active chromophores upon further functionalization.

show abstract

“…The exocyclic PÀR group can be easily tuned by using the particular reactivity of 3,o peningt he way towardf unctionalization of the compounds. [16] These derivatives displayahighly distortedp olicyclic backbone.P hotophysicals tudies revealed that thesec om- Figure 4. OLED spectra recorded at 30 mA cm À2 for different doping rates.…”

Section: Resultsmentioning

confidence: 99%

“…PÀC1 []1 .787(4)1 .782(15) PÀC6 []1 .801(4)1 .777 (14) C1ÀC2 []1 .441 (5) 1.426 (2) C2ÀC3 []1 .426 (5) 1.441 (2) C3ÀC4 []1 .513 (5) 1.514(18) C4ÀC5 []1 .422 (5) 1.445 (19) C5ÀC6 []1 .426 (5) 1.435(2) C1-P-C6 [8]1 10.99 (16) 107.54 (7) C13-C3-C4-C20[8]3 8.80 (5) 30.40 (18) distorted nature of the polycyclic framework in 6-8 is also verified by DFT calculations in the gas phase and the calculated characteristic distances and angles clearly match the experimental data obtained from X-ray diffraction (for detailss ee the Supporting Information). Despite the distortion of the backbone, p-dimers (d = 3.57 )a re observeda long the b axis in the packing.…”

mentioning

confidence: 99%

Naphthyl-Fused Phosphepines: Luminescent Contorted Polycyclic P-Heterocycles

Delouche¹,

Mokrai²,

Roisnel³

et al. 2019

Preprint

View full text Add to dashboard Cite

This article presents the synthesiso fanew family of naphthyl-fused phosphepines through Ni-mediated CÀC coupling. Interestingly,t he chlorophosphine oxide intermediate shows strong resistance toward oxidation/hydrolysis owing to ac ombination of steric hindrance and pnictogen interactions. However,i tc an undergo substitution reactions under specific conditions. The optical/redox properties and the electronic structureo ft hese new p-systems were stud-ied experimentally (UV/Vis absorption, emission, cyclic voltammetry) and computationally (TD-DFT calculations, NICS investigation). Ta king advantage of the luminescence of these derivatives, ab lue-emittingO LED hasb een prepared, highlighting that these novel p-conjugated P-heterocycles appear to be promising buildingb locks for solid-state lighting applications.[a] T.[**] Ap revious versiono ft his manuscripth as been deposited on ap reprint server (https://doi.org/10.26434/chemrxiv.9892001.v1).Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

show abstract

Dithienophosphole‐Based Phosphinamides with Intriguing Self‐Assembly Behavior

Cited by 37 publications

References 27 publications

Intramolecular Phosphacyclization: Polyaromatic Phosphonium P‐Heterocycles with Wide‐Tuning Optical Properties

Intramolecular Phosphacyclization: Polyaromatic Phosphonium P‐Heterocycles with Wide‐Tuning Optical Properties

Organic Electron Acceptors Comprising a Dicyanomethylene‐Bridged Acridophosphine Scaffold: The Impact of the Heteroatom

Naphthyl-Fused Phosphepines: Luminescent Contorted Polycyclic P-Heterocycles

Contact Info

Product

Resources

About