Organophosphorus π-Conjugated Materials

Baumgartner, Thomas; Réau, Régis

doi:10.1021/cr040179m

Cited by 1,013 publications

(412 citation statements)

References 413 publications

Supporting

Mentioning

399

Contrasting

Unclassified

Order By: Relevance

“…By exploiting organic synthetic tools,21, 22 one can tune the molecular HOMO–LUMO gap8 by 1) changing the size and edge of the carbon‐based aromatic framework; 2) varying the molecular planarity upon insertion of bulky substituents or bridging chains; 3) changing the aromatic properties of the constituent monomeric units; 4) varying the peripheral functionalization through the insertion of electron‐donating or electron‐ withdrawing substituents; 5) enclosing structural defects; 6) promoting supramolecular interactions between individual molecules governing their organization into a condensed phase, and 7) replacing selected carbon atoms by isostructural and isoelectronic analogues (i.e., doping). In particular, the heteroatom‐doping approach23, 24 is increasingly becoming important, as significant perturbation of the optoelectronic properties can be obtained without a substantial structural modification 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36…”

Section: Introductionmentioning

confidence: 99%

Tailoring Colors by O Annulation of Polycyclic Aromatic Hydrocarbons

Miletić

Fermi

Orfanos

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

The synthesis of O‐doped polyaromatic hydro‐ carbons in which two polycyclic aromatic hydrocarbon sub units are bridged through one or two O atoms has been achieved. This includes high‐yield ring‐closure key steps that, depending on the reaction conditions, result in the formation of furanyl or pyranopyranyl linkages through intramolecular C−O bond formation. Comprehensive photophysical measurements in solution showed that these compounds have exceptionally high emission yields and tunable absorption properties throughout the UV/Vis spectral region. Electrochemical investigations showed that in all cases O annulation increases the electron‐donor capabilities by raising the HOMO energy level, whereas the LUMO energy level is less affected. Moreover, third‐order nonlinear optical (NLO) measurements on solutions or thin films containing the dyes showed very good values of the second hyperpolarizability. Importantly, poly(methyl methacrylate) films containing the pyranopyranyl derivatives exhibited weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, and thus revealed them to be exceptional organic materials for photonic devices.

show abstract

Section: Introductionmentioning

confidence: 99%

Tailoring Colors by O Annulation of Polycyclic Aromatic Hydrocarbons

Miletić

Fermi

Orfanos

et al. 2017

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Phospholes, in particular, possess unique electronic and structural features that have made them a particularly intriguing research focus 1a–1d. In this context, we introduced self‐assembled ionic phosphole lipids in 2011 2.…”

mentioning

confidence: 99%

Dithienophosphole‐Based Phosphinamides with Intriguing Self‐Assembly Behavior

2016

Self Cite

View full text Add to dashboard Cite

A new, highly adaptable type of phosphinamide‐based hydrogen bonding is representatively demonstrated in π‐conjugated phosphole materials. The rotational flexibility of these intermolecular P=O−H−N hydrogen bonds is demonstrated by X‐ray crystallography and variable‐concentration NMR spectroscopy. In addition to crystalline compounds, phosphinamide hydrogen bonding was successfully introduced into the self‐assembly of soft crystals, liquid crystals, and organogels, thus highlighting the high general value of this type of interaction for the formation of organic soft materials.

show abstract

“…[1][2][3][4][5][6] Among these, the transition-metal-catalyzed crosscoupling reaction is one of the most practical methods in modern organic syntheses. [7][8][9] With regard to the synthesis of arylphosphonates, the Pd-catalyzed cross-coupling reactions of aryl halides with dialkyl H-phosphites (i.e., Hirao P-arylation) have proved to be a powerful method.…”

mentioning

confidence: 99%

Pd-Catalyzed P-Arylation of Triarylantimony Dicarboxylates with Dialkyl H-Phosphites without a Base: Synthesis of Arylphosphonates

Matsumura

Dong

Kakusawa

et al. 2015

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

The reaction of triarylantimony diacetates [Ar 3 Sb(OAc) 2 ] with dialkyl H-phosphites [H-PO(OR)2] in the presence of a Pd(PPh 3 ) 4 (5 mol%) catalyst led to the formation of arylphosphonates in moderate to excellent yield under base-free conditions. This reaction is the first example of carbon-phosphorus bond formation by using an organoantimony compound as a pseudo-halide.Key words Hirao-type P-arylation; triarylantimony diacetate; arylphosphonate; dialkyl H-phosphite; basefree reaction Phosphorus-carbon (P-C) bond formation for the synthesis of organophosphorus compounds is a fundamental and significant research topic in organic synthesis, materials, and biology.1-6) Among these, the transition-metal-catalyzed crosscoupling reaction is one of the most practical methods in modern organic syntheses. [7][8][9] With regard to the synthesis of arylphosphonates, the Pd-catalyzed cross-coupling reactions of aryl halides with dialkyl H-phosphites (i.e., Hirao P-arylation) have proved to be a powerful method. [10][11][12][13][14][15][16][17][18][19][20][21] The general procedure of these P-arylations involves a Pd-phosphine complex as the catalyst with the use of a stoichiometric or an excess amount of a base. Recently, different aryl substances were investigated for their reactivity with phosphorus agents. Sulfonates, 22,23) diaryliodonium salts, 24) arylboronic acids, 25) aryldiazonium salts, 26) and triarylbismuthanes 27) have been reported to be useful for P-C bond formation as the arylating reagents with dialkyl H-phosphites; however, a base and/or an additive was required for the transformation.On the other hand, Pd-catalyzed cross-coupling reactions using organoantimony compounds have recently been the focus of attention. Triarylantimony dicarboxylates act as effective arylating agents in Pd-catalyzed C-C(Ar) bond formation reactions such as [28][29][30] 31) and Hiyama-type 32) reactions. Over the past few years, we have also found that they are an efficient aryl donors in base-free Suzuki-type reactions and copper-and base-free Sonogashira-type reactions. [33][34][35] Moreover, base-free Miyaura-type cross-coupling reactions for boron-carbon (B-C) bond formation using triarylantimony diacetates and tetra(alkoxo) diborons afforded the corresponding arylboronates.36) As a continuation of our studies on heteroatom-carbon bond formation, we now report a novel Pd-catalyzed Hirao-type P-arylation of a pentavalent organoantimony compound, triarylantimony diacetate, with dialkyl H-phosphites afford to the corresponding arylphosphonates without using any base. Results and DiscussionWe initially focused our attention on the determination of the optimum conditions for the P-arylation of organoantimony(V) and bismuth(V) compounds (1a-8) with diethyl phosphite (9a) without using a base. The results including the search for active substrates, optimum amount of phosphorus reagent and suitable catalysts for the reaction are summarized in Table 1. The progress of the reaction was monitored by gas-liquid chromatography (GLC) an...

show abstract

Organophosphorus π-Conjugated Materials

Abstract: International audienc

Cited by 1,013 publications

References 413 publications

Tailoring Colors by O Annulation of Polycyclic Aromatic Hydrocarbons

Tailoring Colors by O Annulation of Polycyclic Aromatic Hydrocarbons

Dithienophosphole‐Based Phosphinamides with Intriguing Self‐Assembly Behavior

Pd-Catalyzed P-Arylation of Triarylantimony Dicarboxylates with Dialkyl H-Phosphites without a Base: Synthesis of Arylphosphonates

Contact Info

Product

Resources

About