Phosphorus Heterocycles

Iaroshenko, Viktor O.; Mkrtchyan, Satenik

doi:10.1002/9783527672240.ch8

Cited by 19 publications

(18 citation statements)

References 454 publications

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“…Generally, strong electron-withdrawing and/or sterically bulky ligands impart geometric constraints that in turn generate reactive 4SQ sites for use in main group catalysis. ,, However, the Lewis acidity of these hypervalent phosphorus centers arises from the preferred formation of two 3c–4e bonds with moderate strength in 4SQ over a single, strong 3c–4e bond in the corresponding 3BP geometry. While the 4SQ geometry is slightly energetically favored over 3BP, these compounds dynamically exchange between these two geometries in solution, not unlike the Berry pseudorotation mechanism invoked for other pentacoordinate main group species. ,, The 4SQ geometry is desirable in the solid state as this allows for a parallel arrangement between the extended conjugated scaffolds of adjacent molecules to enhance their intermolecular π–π interactions, which in turn mutually protect the neighboring phosphorus centers from exposure to nucleophiles (Figure , inset). It is noteworthy that this interaction persists not only in the solid state but also in solution at very low concentrations.…”

Section: Altering the σ*−π* Interaction Through Hypervalencymentioning

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: Altering the σ*−π* Interaction Through Hypervalencymentioning

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%

Unique Phosphorus-Based Avenues for the Tuning of Functional Materials

2023

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“…Phosphorus containing heterocycles can be subdivided by coordination number, with three coordinate and four coordinate geometries (σ 3 , σ 4 ) being the most commonly studied systems. 18–24 In particular, σ 3 ,λ 3 -phospholes have drawn much attention, as their (i) trigonal pyramidal geometry and reduced aromaticity allow for unusual means to tune electronic delocalization into the π-system, and (ii) the lone pair on phosphorus offers additional opportunities to modulate HOMO and LUMO levels. Specifically, chemical modification of the P atom by oxidation, alkylation, or coordination by Lewis acids and metals has led to tunable new π-conjugated systems with diverse photophysical properties.…”

Section: Introductionmentioning

confidence: 99%

Luminescent 1H-1,3-benzazaphospholes

et al. 2023

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“…Over the past few decades, the organophosphorus chemistry field has witnessed a growing research interest since organophosphorus compounds have found widespread applications in medicinal chemistry, organometallic chemistry, agricultural chemistry, and materials chemistry. 1 Specifically, phosphorodithioate compounds bearing the thiophosphoryl bond have useful properties such as insecticides (Fig. 1, A and B ) and neurotoxins (Fig.…”

Section: Introductionmentioning

confidence: 99%