Synthesis of a Trivalent <i>P</i>‐Chloro‐Dithienophosphole and Its Reactivity with Organometallic Reagents

Gaffen, Joshua R.; Wang, Zisu; Baumgartner, Thomas

doi:10.1002/ejic.201801229

Cited by 6 publications

(2 citation statements)

References 29 publications

(45 reference statements)

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“…This implies that the bulky substituents affected the structures in the excited states. In the case of phospholes, it was reported that bulky substituents on the phosphorus atoms caused minor change in the absorption maxima, 18 but the effects on the structural relaxation were not discussed. To understand this phenomenon, the full geometries of 2 and 6 in their singlet excited (S 1 ) states were optimized at B3LYP/6-31G+(d,p), and were compared with those in their S 0 states (Fig.…”

Section: Resultsmentioning

confidence: 99%

4-Aryldithieno[3,2-b:2′,3′-d]arsoles: effects of the As-substituent on the structure, photophysical properties, and stability

et al. 2022

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Section: Resultsmentioning

confidence: 99%

4-Aryldithieno[3,2-b:2′,3′-d]arsoles: effects of the As-substituent on the structure, photophysical properties, and stability

et al. 2022

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“…For example, compound 4 can be treated with organometallic reagents, such as Grignard and organolithium species, to afford dithienophospholes with a variety of P–R groups ( 5 , 5-O ) (Scheme ). − …”

Section: Enhancing σ*−π* Interactions Through P–p Bond Formationmentioning

confidence: 99%

Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

2023

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Metrics & MoreArticle Recommendations CONSPECTUS: Recent ground-breaking advances in synthetic chemistry have transformed main-group molecules from simple laboratory curiosities into powerful materials for a range of applications in all realms of life. Electron-accepting or -deficient materials, in particular, have been the focus of development since their generally limited availability and stability have been major hurdles in establishing new practical applications. In addition to the general requirements for the design of these materials, a deeper understanding of their inherent electronics and molecular interactions is a requirement for the successful expansion of their utility. Previously, the incorporation of electron-deficient main-group elements, such as boron, into a conjugated organic framework was considered to be an effective route toward the synthesis of high-performing electron-accepting materials. However, challenging conditions such as the need for bulky substituents for kinetic stabilization, air-free and moisture-sensitive synthesis, and restricted storage abilities have led to the investigation of other elements across the periodic table to be used in a similar vein. Lately, heavier main-group elements such as Si, Ge, P, As, Sb, Bi, S, Se, and Te have also proven to be advantageous for electron-accepting materials as they exhibit polarizable molecular orbitals that are easily accessible to electrons or nucleophiles. This has laid the foundation for materials chemistry research on a variety of applications, including optoelectronic devices such as OLEDs, organic photovoltaics, energy storage such as in batteries and capacitors, fluorescent sensors with both biological and physiological applications, organocatalysis and synthesis, and many more. Among the main-group-element-based materials, organophosphorus species are privileged as their frontier orbitals are easily altered by chemical modification or/and structural and geometrical manipulations at the phosphorus center itself, without the need for kinetic stabilization, or through electronic modification of the conjugated system. The five-membered phosphorus-based heterocycle, phosphole, is a particularly interesting motif in this context, and extensive studies on the corresponding materials have uncovered the rich fundamentals of the σ*−π* interaction that imparts intriguing accepting properties while sustaining morphological and physiological stability for utilization in real-life scenarios. Moreover, beyond the σ*−π* interaction in phospholes that is key to many of their acceptor properties as a material, the use of phosphorus also gives rise to easily accessible, low-lying antibonding orbitals. They pave the way for Lewis acid phosphorus species that, despite being considered to be electron-rich species in general, open up several possibilities for intriguing chemical reactivity through hypervalency. Herein, we representatively discuss some recent advancements through the various approaches that leverage the unique structures and electronics...

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Tricyclic-fused bithiophenes and related analogues: Important building blocks for conjugated materials

Rasmussen

Uzelac

Culver

2020

Advances in Heterocyclic Chemistry

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Synthesis of a Trivalent P‐Chloro‐Dithienophosphole and Its Reactivity with Organometallic Reagents

Cited by 6 publications

References 29 publications

4-Aryldithieno[3,2-b:2′,3′-d]arsoles: effects of the As-substituent on the structure, photophysical properties, and stability

4-Aryldithieno[3,2-b:2′,3′-d]arsoles: effects of the As-substituent on the structure, photophysical properties, and stability

Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

Tricyclic-fused bithiophenes and related analogues: Important building blocks for conjugated materials

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