Functional small-molecules &amp; polymers containing PC and AsC bonds as hybrid π-conjugated materials

Salazar, Daniel Morales; Mijangos, Edgar; Pullen, Sonja; Gao, Ming; Orthaber, Andreas

doi:10.1039/c6cc08736a

Cited by 43 publications

(34 citation statements)

References 26 publications

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“…Analogues of alkenes with arsenic atoms, arsaalkenes, are attractive for the incorporation of arsenic atoms into π‐conjugated systems, whereas trigonal pyramidal arsenic atoms tend to inhibit effective π conjugation. The group of Orthaber reported electropolymerization of arsaalkene monomer 46 , which was synthesized from arsaalkene 45 by Stille coupling (Scheme ) . The LUMOs of arsaalkene small molecules 45 and 46 and polymer 47 correspond to the fulvene core π* orbitals, including the arsenic atoms, although the HOMOs were delocalized across the fluorenylidene–thienyl backbones.…”

Section: Conjugated Polymersmentioning

confidence: 99%

The Dawn of Functional Organoarsenic Chemistry

Imoto

Naka

2018

Chemistry A European J

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Organoarsenic chemistry was actively studied until the middle of 20th century. Although various properties of organoarsenic compounds have been computationally predicted, for example, frontier orbital levels, aromaticity, and inversion energies, serious concern to the danger of their synthetic processes has restricted experimental studies. Conventional synthetic routes require volatile and toxic arsenic precursors. Recently, nonvolatile intermediate transformation (NIT) methods have been developed to safely access functional organoarsenic compounds. Important intermediates in the NIT methods are cyclooligoarsines, which are prepared from nonvolatile inorganic precursors. In particular, the new approach has realized experimental studies on conjugated arsenic compounds: arsole derivatives. The elucidation of their intrinsic properties has triggered studies on functional organoarsenic chemistry. As a result, various kinds of arsenic-containing π-conjugated molecules and polymers have been reported for the last few years. In this minireview, progress of this recently invigorated field is overviewed.

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Section: Conjugated Polymersmentioning

confidence: 99%

The Dawn of Functional Organoarsenic Chemistry

Imoto

Naka

2018

Chemistry A European J

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“…On the other hand, phosphinidene units incorporated as phosphaalkenes into π‐conjugated linear oligomers and radialenes have also shown a strong electron‐accepting character . Despite the recent interest in arsoles, such heavier alkenes, that is, arsaalkenes, are scarcely explored in this context . Compounds with double bonds between heavier main‐group elements require kinetic stabilization through sterically demanding substituents to prevent unwanted polymerization or the reaction with small molecules.…”

Section: Figurementioning

confidence: 99%

“…Dibenzofulvenoids with bridgehead E=P and As substituents. ( E ) . Heterofulvenoid CPDT derivatives explored in this work: AsA , PA , and PA‐AuCl .…”

Section: Figurementioning

confidence: 99%

“…[18] The cathodic scans of our systems show an irreversible oxidation at 0.94 Vf or PA and0 .87 Vf or AsA with two additional features at around + 0.5 and + 0.35 V during the anodic scan direction, indicative of polymer deposition. [12] The gold-substituted complex PA-AuCl shows an irreversible reductiona ts low scan rates,w hich becomes quasi-reversible (E 1/2 = À1.56 V) at higher scan rates (n = 1Vs À1 )b esides an irreversible oxidationat0 .68 V.…”

mentioning

confidence: 96%

“…[10] Despite the recent interest in arsoles, such heavier alkenes, that is, arsaalkenes, [11] are scarcely explored in this context. [12] Compoundsw ith double bonds between heavierm aingroupe lements requirek inetic stabilization throughs terically demanding substituents to prevent unwanted polymerization or the reaction with small molecules. In this work, we present very robust derivatives that have been obtained using Mes* (= 2,4,6-tris-tert-butyl phenyl), as in the air-a nd moisture-stable diphosphene Mes*-P=P-Mes*, [13] the structurally related fluorene-based heterofulvene, [11] the non-annulated 2,5-diphenyl phospha-pentafulvene, [14] and otherr elated heterofulvenoid structures.…”

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confidence: 99%

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Synthesis and Characterization of Cyclopentadithiophene Heterofulvenes: Design Tools for Light‐Activated Processes

Nahhas

Shameem

Chábera

et al. 2017

Chemistry A European J

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The development of new materials for solar-to-energy conversion should consider stability, ease of fabrication, and beneficial photophysical properties. In this context, a set of novel π-conjugated building blocks, with phospha- and arsaalkenes possessing a unique dithienyl annulated heterofulvenoid core, have been prepared as air- and moisture-stable sensitizers. These compounds unify electron-donor and -acceptor moieties, making them potential candidates for light-harvesting applications. Optical characterization of these systems was performed by steady-state and time-resolved absorption spectroscopy, supported by time-dependent DFT calculations. Tuning of the optical properties of these systems can be achieved by varying the pnictogen element at the bridgehead position, giving a bathochromic shift of ≈40 nm and coordinating the phosphaalkene towards gold Au centers. The latter results in a ≈2000-fold extension of the ≈10 ps lifetime of uncoordinated systems well into the ns regime.

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Organophosphorus Polymers

Green

Orthaber

2019

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This article discusses polymers containing phosphorus centers that impart essential properties, functions, and responses to the discussed materials. By incorporating this heteroelement, the toolbox for tailoring optical, electronic, and structural properties as well as chemical reactivity is greatly expanded over “carbon” analogs. We discuss unsaturated (e.g., phosphaalkenes), saturated (e.g., phosphine oxides), and cyclic (e.g., phospholes) phosphorus motifs incorporated into conjugated polymers. Such organophosphorus systems are believed to have a bright future in optoelectronic devices, with this being demonstrated in organic light‐emitting diodes as acceptor and emitter materials, and in fundamental studies as responsive sensor systems. Saturated organophosphorus polymers allow for chemical transformations at the phosphorus centers by means of oxidation, metal (Lewis acid) coordination, quaternization, and so on. These modifications and transformations are used in sensing, scavenging, and catalytic systems. Moreover, in this article, we cover selected inorganic polymers, that is, polymers having exclusively inorganic skeletal atoms. These mainly include the polyphosphine and phosphinoborane classes of materials, for which recent fundamental studies have illustrated their potential as ceramic precursors. Polymerization methods are often similar to those applied in organic polymers, but a large variety of polymerizations have also been specifically developed for phosphorus and other pnictogens, and these have also been employed to synthesize these fascinating materials.

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Functional small-molecules & polymers containing PC and AsC bonds as hybrid π-conjugated materials

Cited by 43 publications

References 26 publications

The Dawn of Functional Organoarsenic Chemistry

The Dawn of Functional Organoarsenic Chemistry

Synthesis and Characterization of Cyclopentadithiophene Heterofulvenes: Design Tools for Light‐Activated Processes

Organophosphorus Polymers

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