Materials Containing Homocatenated Polysilanes

Sanji, Takanobu

doi:10.1002/9781119235941.ch8

Cited by 5 publications

(7 citation statements)

References 101 publications

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“…Heteroatom-incorporated conjugated materials are an attractive avenue toward electron-acceptor species as they offer unique opportunities for the tuning of optoelectronic, electrochemical, and structural properties. Moreover, heteroatom incorporation can also afford Lewis acid compounds with utility as reagents and catalysts for chemical transformations in organic synthesis. , …”

Section: Introductionmentioning

confidence: 99%

“…This and the overall lower orbital energies potentially make antibonding orbitals of the heavier main-group elements available for an interaction with a π-scaffold or a σ-donor. The case of phosphorus is an excellent representative example in this context …”

Section: Introductionmentioning

confidence: 99%

“…This is true for the five-membered phosphorus ring systems as well. Phosphole, a relative of pyrrole, is considered to be only slightly aromatic by virtue of the pyramidal P atom while the latter are inherently planar and have more pronounced aromatic character …”

Section: Introductionmentioning

confidence: 99%

“…This allows installing a second exocyclic P substituent that, with its inherent P–E σ* orbital, can engage in a second σ*−π* interaction, thus further lowering the energy level of the LUMO (Figure ). − ,, …”

Section: Introductionmentioning

confidence: 99%

“…Nevertheless, the dithieno[3,2- b ;2′,3′- d ]heteroles II – IV shown in Chart are thermodynamically stable and exhibit phosphorescence that has not been seen for the P-containing relatives to date. The heavier pnictogens also resist oxidation due to the stronger s-character of their lone pair, while the phosphorus congener is readily oxidized, affording a new functionalization avenue for tuning the electronic properties of these systems . Additionally, larger phosphorus ring systems, such as phosphepines ( V ), have similarly pronounced optical properties as their five-membered congeners but are synthetically less accessible than dithienophospholes. , …”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

2023

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Funktionelle polymere Materialien auf der Basis von Hauptgruppen‐Elementen

Vidal

Jäkle

2019

Angewandte Chemie

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In den letzten zehn Jahren wurden enorme Fortschritte bei der Synthese von Polymeren erzielt, die Hauptgruppen‐Elemente enthalten und über die typischen organischen Polymere hinausgehen. Einzigartige Eigenschaften, die sich aus drastischen Unterschieden in Bindung und molekularer Geometrie, elektronischer Struktur und chemischer Reaktivität ergeben, werden in den unterschiedlichsten Anwendungsbereichen genutzt. In dem Aufsatz werden die jüngsten Fortschritte bei Polymeren mit anorganischem Rückgrat hervorgehoben, es wird diskutiert, wie die Lewis‐Säure/Base‐Funktionalisierung von Polymeren zu beispielloser Reaktivität führt, und es werden konjugierte Hybride mit spezifischen elektronischen Strukturen für die Sensorik sowie Anwendungen in Organische‐Elektronik‐Geräten vorgestellt.

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Functional Polymeric Materials Based on Main‐Group Elements

2019

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The past decade has witnessed tremendous advances in the synthesis of polymers that contain elements from the main groups beyond those found in typical organic polymers. Unique properties that arise from dramatic differences in bonding and molecular geometry, electronic structure, and chemical reactivity, are exploited in diverse application fields. Herein we highlight recent advances in inorganic backbone polymers, discuss how Lewis acid/base functionalization of polymers results in unprecedented reactivity, and survey conjugated hybrids with unique electronic structures for sensor and device applications.

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Materials Containing Homocatenated Polysilanes

Cited by 5 publications

References 101 publications

Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

Funktionelle polymere Materialien auf der Basis von Hauptgruppen‐Elementen

Functional Polymeric Materials Based on Main‐Group Elements

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