This review serves as a brief introduction to phospholes and discusses their unique favorable properties for application in organic electronic materials. Over the past several years, π-conjugated phospholes have been slowly making their way into devices. We report here the mode of synthesis of these π-conjugated phospholes as well as discuss the performances of the devices.

/pdf/p-conjugated-phospholes-and-their-incorporation-into-devices-339w1omtyi.pdf

π-Conjugated phospholes and their incorporation into devices: components with a great deal of potential

Degradation of proteins by PROTACs and other strategies.

https://iopscience.iop.org/article/10.1070/RCR4795/pdf

Organofluorine chemistry: promising growth areas and challenges

Phosphorus, Sulfur, and Silicon and the Related Elements

The aim of this work is to convince practitioners of 31P NMR methods to regard simple GIAO quantum chemical calculations as a safe tool in structural analysis of organophosphorus compounds. A comparative analysis of calculated GIAO versus experimental 31P NMR chemical shifts (CSs) for a wide range of phosphorus containing model compounds was carried out. A variety of combinations (at the HF, DFT (B3LYP and PBE1PBE), and MP2 levels using 6-31G(d), 6-31+G(d), 6-31G(2d), 6-31G(d,p), 6-31+G(d,p), 6-311G(d), 6-311G(2d,2p), 6-311++G(d,p), 6-311++G(2d,2p), and 6-311++G(3df,3pd) basis sets) were tested. On the whole, it is shown that, in contrast to what is claimed in the literature, high level of theory is not needed to obtain rather accurate predictions of 31P CSs by the GIAO method. The PBE1PBE/6-31G(d)//PBE1PBE/6-31G(d) level can be recommended for express estimation of 31P CSs. The PBE1PBE/6-31G(2d)//PBE1PBE/6-31G(d) combination can be recommended for routine applications. The PBE1PBE/6-311G(2d,2p)//PBE1PBE/6-31+G(d) level can be proposed to obtain better results at a reasonable cost. Scaling by linear regression parameters significantly improves results. The results obtained using these combinations were demonstrated in 31P CS calculations for a variety of medium (large) size organic compounds of practical interest. Care has to be taken for compounds that may be involved in exchange between different structural forms (self-associates, associates with solvent, tautomers, and conformers). For phosphorus located near the atoms of third period elements ((CH3)3PS and P(SCH3)3) the impact of relativistic effects may be notable.

/pdf/quantum-chemical-calculations-of-31p-nmr-chemical-shifts-43wnxss38h.pdf

Quantum chemical calculations of 31P NMR chemical shifts: scopes and limitations

Phospholes – Development and Recent Advances

Major tendencies in modern chemistry of alkali and transition metal phospholides (phosphacyclopentadienides) are systematized, analyzed and generalized. Basic methods of synthesis of these compounds are presented. Their chemical properties are considered with a special focus on their complexing ability. Potential applications of phospholides and their derivatives are discussed. The bibliography includes 184 references.

https://iopscience.iop.org/article/10.1070/RC2014v083n06ABEH004442/pdf

Alkali and transition metal phospholides

The strength of conjugation between the diene moieties of 1-R-1,2-diphospholes and 1-R-phospholes and exocyclic phenyl groups of these P-heteroles has been quantitatively characterized by the use of Raman activities of the bands of the phenyl substituents. It is shown that conjugation in both types of phospholes is very similar to the conjugation of phenyl groups with the diene system of cyclopentadiene. Introduction of substituents (−OMe, −C(═O)H, −NO2, −NMe2, and −CH═CH2) in the para-position of the phenyl groups of 1-R-1,2-diphospholes extends π-delocalization of exocyclic groups into the electronic system of the 1,2-diphosphole ring, producing bathochromic shifts of the absorption bands up to 63 nm. In contrast, hypsochromic shifts up to 40 nm can be achieved by introduction of SnMe3 or SiMe3 groups at the phosphorus(III) atom of the 1,2-diphosphole and concomitant increase of aromaticity of the P-heterole. Conjugation shifts the “centre of gravity” of the whole electronic absorption spectrum, whereas...

Conjugation in and optical properties of 1-R-1,2-diphospholes and 1-R-phospholes.

Twenty 3,4,5-triaryl-1-R-1,2-diphospholes were studied within the framework of density functional theory (DFT) and experimentally by UV/vis spectroscopy to check their suitability for opto-electronic applications. Time-dependent DFT (TD-DFT) calculations employing the PBE0 hybrid density functional combined with moderately sized def-TZVP basis set were shown to excellently reproduce the experimental absorption spectra of various 1,2-diphospholes. Frontier molecular orbital analysis reveals that HOMO and LUMO are mainly localized on the diphosphole ring and, to some extent, on the aryl moieties. The HOMO–LUMO energy gap can be easily tuned by variation of substituents introduced in para-positions of the aryl moieties and, to a lesser extent, by modification of the R group at phosphorus atom. As a result, both position and intensity of the absorption bands with highest wavelength are strongly influenced by the above structural changes. The UV-spectra simulations reveal that the introduction of donor groups ...

Application of Time-Dependent Density Functional Theory and Optical Spectroscopy toward the Rational Design of Novel 3,4,5-Triaryl-1-R-1,2-diphospholes

Almaz Zagidullin

Papers

Phospholes – Development and Recent Advances

Alkali and transition metal phospholides

Conjugation in and optical properties of 1-R-1,2-diphospholes and 1-R-phospholes.

Application of Time-Dependent Density Functional Theory and Optical Spectroscopy toward the Rational Design of Novel 3,4,5-Triaryl-1-R-1,2-diphospholes

Cycloaddition Reactions of 1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes