Synthesis of a Luminescent Azaphosphole

Wu, Shaoteng; Rheingold, Arnold L.; Golen, James A.; Grimm, Alexandra B.; Protasiewicz, John D.

doi:10.1002/ejic.201501279

Cited by 26 publications

(8 citation statements)

References 75 publications

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“…In recent decades, much attention has been paid to phosphole- and heterophosphole-containing materials because they have great potential for applications in electronic devices such as photovoltaic cells, organic or polymer light-emitting diodes (OLEDs or PLEDs, respectively), polymeric sensors, and organic thin-film transistors (OTFTs). − Organic materials used in electronic devices can be divided into two main types in terms of their reduction of the HOMO–LUMO energy gap. The first type is based on π-conjugated oligomers, while the second type contains charge transfer complexes.…”

Section: Introductionmentioning

confidence: 99%

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

et al. 2020

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Herein, we present the synthesis, single-crystal X-ray structures, and spectroscopic properties for the 1:1 donor−acceptor complexes of 1,2,4,5-tetracyanobenzene (TCNB) with annelated 3a,6a-diaza-1,4-diphosphapentalenes (DDPs) based on cyclohexanone azine (2) and tetralone azine (4). These are the first complexes of an organic π-acceptor with donor phosphorus heterocycles. According to the X-ray study, the DDPs and TCNB molecules are alternately stacked with interplanar distances of 3.335 and 3.404 Å for 2 and 4, respectively, which are suitable for intermolecular π•••π interactions. The bond lengths and angles in the component molecules agree with values for neutral species, and the infrared spectra indicate a very slight degree of ionicity. The estimated HOMO−LUMO gap from the onset of optical absorption (1.40 eV) is in agreement with the band gap estimated from the density functional theory calculations for 2 (1.47 eV). By contrast, in a reaction with the related electron acceptor, tetrachloroterephthalonitrile, the DDPs proved to be donors of lone electron pairs in a nucleophilic aromatic substitution reaction of chlorine atoms demonstrating the duality of their electronic nature.

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Section: Introductionmentioning

confidence: 99%

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

et al. 2020

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“…But several successful attempts to use R 2 C=PR and RC≡P monomers for the synthesis of conjugated polymers were reported . Compared to the C=C π‐bond, the P=C double bond is significantly weaker and the gap between the π (HOMO) and π*(LUMO) orbitals of the C=P bond is much smaller . Phosphorus‐containing π‐conjugated heterocycles are often easier to handle, and sodium phosphaethynolate, Na(OCP), proved to be a versatile building block for those (see selected examples in Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Annulated 1,3,4‐Azadiphospholides: Heterocycles with Widely Tunable Optical Properties

2017

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Phosphorus heterocycles find applications in the synthesis of p-conjugated compounds and as precursors for optoelectronic materials such as organic light-emitting diodes (OLEDs), electronic switches,a nd transistors.Ahigh-yield, one-pot synthesis of anionic annulated 1,3,4-azadiphospholides from Na(OCP) and 2-chloropyridines is presented. The synthesis proceeds without the use of transition metals and tolerates aw ide range of substrates.C yano-substituted compounds are especially deeply colored and have absorption maxima which range from l max = 525 to 596 nm. The optical properties are dominated by the spatial separation of an electron acceptor and donor unit within one molecule (pushpull chromophore). The anionic 1,3,4-azadiphospholides are silylated to neutral siloxy compounds with astrong blue-shifted absorption. This reaction can be reversed by addition of fluoride ions,w hich allows fluoride ions to be detected in optically lowc oncentrations.Numerous p-conjugated molecules have astrong impact in the studies of new organic semiconductors and materials,such as dyes in lasers, [1] sensors,l ight emitting diodes, [2] and components for solar cells.[3] Introduction of main group elements in the extended p-systems such as sulfur, [4] boron, [5] silicon, [6] arsenic, [7] and phosphorus [8] allow the physical and electronic properties to be tuned.[9] Unsaturated molecules with low-valent s 2 ,l 3 -phosphorus centers have at endencyt o oligomerize and/or form cage-compounds,l imiting their application.[10] But several successful attempts to use R 2 C= PR and RCPm onomers for the synthesis of conjugated polymers were reported. [11] Compared to the C = C p-bond, the P = Cdouble bond is significantly weaker and the gap between the p (HOMO) and p*(LUMO) orbitals of the C = Pb ond is much smaller. [9g, 12] Phosphorus-containing p-conjugated heterocycles are often easier to handle, [8] and sodium phosphaethynolate,N a(OCP), proved to be av ersatile building block for those (see selected examples in Scheme 1). )o r[ 2 + +4] cycloadditions (VI [15] ), respectively,w hich are likewise formed by incorporating ac omplete (OCP) À anion into the cycle.[14c]Thef ive-membered heterocycles VII-IX are special because they are formed in reactions between carboxylic acid chloride derivatives,RC(= X)Cl (X = NR, O, S) with two (OCP) À anions,but only one is fully included while the other serves as source of a" P À "i on after loss of CO.[17] Herein we report as imple access to annulated 1,3,4-azadiphospholes with aw idely tunable p-conjugated electronic structure, which have,i nc ontrast to well-studied diazaphospholes, [18] only rarely been investigated before. [19] These new compounds may find applications in electronic devices or chemical sensors.We first further improved the synthesis of Na(OCP), which can now be very easily prepared on aseveral-hundred gram scale in high yield by simply exposing as olution of NaOtBu and dimethylcarbonate in THF to PH 3 (Scheme 2).[20] Subsequently,N a(OCP) was reacted with various 2...

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“…π-Conjugated polymers and materials are highly studied materials for their potential in various optoelectronic applications. Our work has focused on the development of π-conjugated materials involving pπ–pπ PC bonds. − Compounds related by the formal replacement of CC bonds with PC bonds often display similarities in structures and reactivities. These parallels have led to these organophosphorus analogues of unsaturated hydrocarbons to be nicknamed “carbon copies”. − Extended π-conjugated materials having pπ–pπ PC units might thus serve as interesting candidates as materials for possible OLED or OPV applications.…”

Section: Introductionmentioning

confidence: 99%

2-Aryl-1,3-Benzoxaphospholes as Unwilling Participants for Catalytic Suzuki–Miyaura CC Coupling Reactions

et al. 2021

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Under conditions typically effective to achieve a catalytic aryl–aryl bond during palladium Suzuki–Miyaura (SM) coupling reactions of ArB(OH)2 and ArBr, reactions of p-tolylboronic acid and 2-(BrC6H4)-1,3-benzoxaphosphole (BrC6H4-BOP, 1) failed to provide the anticipated product of CC bond coupling, 2-(p-CH3C6H4-C6H4)-1,3-benzoxaphosphole. An analysis of reaction mixtures by 1H and 31P{1H} NMR spectroscopic methods showed the presence of numerous broad resonances, suggesting the formation of labile metal complexes with 1. This possibility was confirmed by determinations of the solid-state structures of [(tBu3P)(Ph-BOP)M]2 (M = Pt, 5; M = Pd, 6) from the reaction of Ph-BOP and [M(tBu3P)2] (M = Pt, Pd). The structures of 5 and 6 are isomorphous and reveal unusual bridging μ2-P-BOP bonding modes. Computational studies have explored the structures and relative energies and indicate that dimeric complexes of this form can dissociate easily. Surprisingly, even when PC double bonds of Ar-BOPs are sheltered by coordination to tungsten pentacarbonyl, the Ar-BOP units resist yielding products of CC coupling under similar SM conditions but instead yield unusual products whereby CsOH adds across the PC bonds in [(CO)5W{2-Ar-BOP}]. Computational studies are consistent with ready addition of hydroxide to the tungsten-protected PC bond.

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Synthesis of a Luminescent Azaphosphole

Cited by 26 publications

References 75 publications

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

Annulated 1,3,4‐Azadiphospholides: Heterocycles with Widely Tunable Optical Properties

2-Aryl-1,3-Benzoxaphospholes as Unwilling Participants for Catalytic Suzuki–Miyaura CC Coupling Reactions

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