Organophosphorus Compounds in Organic Electronics

Shameem, Muhammad Anwar; Orthaber, Andreas

doi:10.1002/chem.201600005

Cited by 213 publications

(95 citation statements)

References 159 publications

(229 reference statements)

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“…As a matter of fact, long lifetimes (usually above 5 ns) are optimum for efficient photo‐induced charge‐transfer events . It is worth noting that, to date, fused phosphorus heterocycles containing pyrrole derivatives have received only little attention …”

Section: Resultsmentioning

confidence: 99%

A Guide for the Design of Functional Polyaromatic Organophosphorus Materials

Hindenberg

López‐Andarias

Röminger

et al. 2017

Chemistry A European J

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The impact of integrating six-membered phosphorus heterocycles into a poly(hetero)aromatic materials is investigated. Mechanistic studies reveal the key synthetic requirements to embed the latter phosphorus heterocycles in polyaromatic molecules. DFT calculations indicate that introducing six-membered phosphorus rings into π-extended molecules induces a particular electron distribution over the π-extended system. Electrochemical investigations confirm that inserting six-membered phosphacycles into polyaromatics triggers ambipolar redox behavior. Steady-state spectroscopy reveals that fusing pyrroles with phosphorus-containing polyaromatic molecules induces fluorescence quantum yields as high as 0.8, whereas transient absorption spectroscopy demonstrates that fusing thiophenes promote the formation of non-emissive triplet-excited states. As a whole, the optoelectronic properties of fused phosphorus-containing materials give rise to promising performances in photoelectrochemical cells. Moreover, X-ray analyses confirm that the 3D arrangement in the solid state of polyaromatic systems containing six-membered phosphorus rings can be tailored through post-functionalization of the phosphorus center. Altogether, this investigation sets the bedrock for the design of a new generation of highly functional polyaromatic organophosphorus materials, keeping control over their electrochemical properties, fluorescence features, photo-induced excited states, and 3D molecular arrangement.

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Section: Resultsmentioning

confidence: 99%

A Guide for the Design of Functional Polyaromatic Organophosphorus Materials

Hindenberg

López‐Andarias

Röminger

et al. 2017

Chemistry A European J

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“…e ANQ geometry for the enol and keto forms was optimized at the DFT level employing the six DFT functionals cited above, the B3LYP showed results with lower deviation between n ⟶ π * and π ⟶ π * and a good agreement with hybrid functional and long-range hybrid functional (CAM-B3LYP and ωB97XD) for the π conjugation [28,[36][37][38]. e B3LYP functional selected in the study was employed for the optimization in the ground state as well as in the theoretical calculations of twenty excited states for all compounds because the first 20 excited states give a good description of the electronic parameters for organophosphorus compounds [36,[39][40][41].…”

Section: Selection Of the Dft Functional For Spectroscopicmentioning

confidence: 68%

Detection of Chemical Weapon Agents Using Spectroscopic Probes: A Computational Study

Braga

Silva

Mancini

et al. 2020

Journal of Chemistry

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Organophosphorus compounds are organic compounds widely employed in agriculture as well as in chemical weapons. The use in agriculture is due to their insecticidal properties. However, in chemical warfare, the use of organophosphorus is associated with acetylcholinesterase inhibition, which promotes the cholinergic syndromes. In this line, the fast detection of this class of compound is crucial for the determination of environmental exposure. This improved detection will naturally allow for more prompt courses of treatment depending on the contaminant findings. In this perspective, the dipyrrinone oxime (1) was employed for the detection of organophosphorus compounds that are employed as nerve agents, such as cyclosarin, sarin, soman, diethyl chlorophosphate, diisopropylfluorophosphate, 2-(dimethylamino)ethyl N,N-dimethylphosphoramidofluoridate, O-ethyl-S-[2-(diethylamino)ethyl]methylphosphonothioate, O-ethyl-S-[2(diisopropylamino)ethyl] methylphosphonothioate, and O,O-diethyl-S-[2-(diethylamino)ethyl] phosphorothioate, through fluorescent emission. The thermodynamics and kinetic parameters as well as spectroscopic properties of the complexes formed for 1 and all organophosphorus compounds previously cited were investigated by means of theoretical calculations. From our findings, only the diethyl chlorophosphate, 2-(dimethylamino)ethyl N,N-dimethylphosphoramidofluoridate, and O,O-diethyl-S-[2-(diethylamino)ethyl] phosphorothioate emitted fluorescence in the hexane, toluene, chloroform, dichloromethane, methanol, acetonitrile, water, and dimethyl sulfoxide solvents. The study of the absorption wavelength with the most polar solvent showed higher values compared to apolar solvents. In the same solvent, for instance, soman in hexane showed the lowest absorption wavelength value, 324.5 nm, and DCP the highest value, 330.8 nm. This behavior was observed in other tested solvents. The thermodynamic parameters indicate negative Gibbs free energy (ΔG) values for the O-ethyl-S-[2(diisopropylamino)ethyl] methylphosphonothioate with 1 reaction. On the other hand, the sarin and cyclosarin revealed the lowest Gibbs free energy (ΔG‡) values, being kinetically favorable and presenting more reactivity.

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“…There is renewed interest– in the fundamental chemistry of phosphorus heterocycles because of their potential for applications as optoelectronic materials, anion sensors, linkers in supramolecular chemistry, and metal‐free catalysts ,. As a result, the stoichiometric and catalytic additions of P−P σ bonds to alkenes, alkynes, and ketones is an area of intensive research .…”

Section: Methodsmentioning

confidence: 99%

Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main‐Group Catalysis

et al. 2017

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The addition of acyclotriphosphine to abroad range of nitriles gives access to the first examples of free 1-aza-2,3,4triphospholenes in ar apid, ambient temperature,o ne-pot, high-yield protocol. The reaction produces electron-rich heterocycles (four lone pairs) and features homoatomic s-bond heterolysis,t herebyc ombining the key features of the 1,3dipolar cycloaddition chemistry of azides and cyclopropanes. Also reported is the first catalytic addition of PÀPbonds to the CNbond. The coordination chemistry of the new heterocycles is explored.

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Organophosphorus Compounds in Organic Electronics

Cited by 213 publications

References 159 publications

A Guide for the Design of Functional Polyaromatic Organophosphorus Materials

A Guide for the Design of Functional Polyaromatic Organophosphorus Materials

Detection of Chemical Weapon Agents Using Spectroscopic Probes: A Computational Study

Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main‐Group Catalysis

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