Non-empirical calculations of the first ionization potential of silatranes and the electronic structure of their radical cations

Belyaeva, V. V.; Frolov, Yulii L.; Воронков, М. Г.

doi:10.3998/ark.5550190.0006.708

Cited by 5 publications

(2 citation statements)

References 12 publications

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“…However, serious difficulties emerged in the interpretation of the energetically lowest part (8-12 eV) of the photoelectron spectra of I. [18][19][20][21][22][23][24] They were caused mainly by the fact that the known procedures for the synthesis and purification of I do not always allow us to deal with the ''ideally'' pure compounds. 18,19,22 Moreover, the photoelectron (PE) spectra of possible impurities (such as a trialkanolamine, the products of its incomplete silylation or the partial hydrolysis of I) and silatranes may overlap.…”

Section: Introductionmentioning

confidence: 99%

“…18,22 Hence, two opposite views on the origin of the first band in the PE spectra of I are known: the band is either due to (i) contamination by impurities; 18,19,22 or (ii) the ionization of silatranes. 20,21,23 A theoretically justified choice in favor of (ii) was made for H-and Me-silatranes by going beyond the vertical picture of their ionization. 24 In the case of molecules XSi(OCH 2 CH 2 ) 3 N, containing principally important substituents X = OAlk, Hal at the silicon atom (which are widely separated from H and Me on an electronegativity A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences Favorsky, 1, Irkutsk 664033, Russian Federation.…”

Section: Introductionmentioning

confidence: 99%

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Assignment of photoelectron spectra of silatranes: first ionization energies and the nature of the dative Si←N contact

Sidorkin

Belogolova

Doronina

2015

Phys. Chem. Chem. Phys.

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The problematic experimental photoelectron spectra of fluoro- and ethoxy-silatranes, XSi[OCH2CH2]3N (X = F and OEt), were assigned using theoretical spectra obtained by combining the OVGF//CCSD vertical ionization energies with the vibrational widths of the electronic transitions (linear vibronic coupling formalism, LVC). Taking into account the overlapping of the silatrane bands with the bands of probable impurities, bicyclic amines, (OH)XSi(OCH2CH2)2NCH2CH2OH, allowed us to reliably determine the position of the low-energy bands (at ∼9.7 eV for F- and at ∼9.2 eV for EtO-silatrane) associated with the ionization from a nitrogen lone pair level. For XSi[OCH2CH2]3N (X = F, H, OEt, Me), the correlation between the first vertical ionization energies, VIEs1, and the geometrical, electronic and orbital characteristics of the Si←N bonding was found. Its analysis suggests that the Si←N coordination in silatranes is orbital-controlled rather than charge-controlled.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Assignment of photoelectron spectra of silatranes: first ionization energies and the nature of the dative Si←N contact

Sidorkin

Belogolova

Doronina

2015

Phys. Chem. Chem. Phys.

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Molecular precursors of mesostructured silica materials in the atrane route: A DFT/GIAO/NBO theoretical study

Fernández

Viruela-Martín

Latorre

et al. 2007

Journal of Molecular Structure: THEOCHEM

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Silatranes: a review on their synthesis, structure, reactivity and applications

2011

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This critical review summarizes progress of the rapidly developing and very active field of silatrane chemistry. The first part of the review deals with general synthetic approaches used to synthesize different silatranes. The most interesting feature of silatranes, i.e., variation of Si-N bond length on the basis of the axial substituent of Si, and other structural features, are described in the second part with special emphasis on crystallographic and theoretical studies. It is followed by a discussion on the reactivity of various silatranes. Silatranes have now gained acceptance for a wide variety of applications which are summarized in the last section of review. Some of them have extensive interest due to their medical use to heal wounds or stimulate hair-growth (pilotropic activity), biological properties, pharmacological properties e.g. antitumor, anticancer, antibacterial, anti-inflammatory, fungicidal activity, stimulating effect in animal production and seed germination effects. The review focuses on the extended potential of silatranes in sol-gel processes, mesoporous zeotypes, atomic force microscopy, commercial products such as adhesion promoters, polymer formation and rubber compositions. This critical review will be helpful for general researchers, experts, advanced undergraduates and newcomers working on silatrane chemistry as this review presents greater emphasis on synthesis and characterization, structural properties, reactivity and applications of silatranes in the field of biology, material science, sol-gel chemistry, pharmaceutics, agriculture and medicine (311 references).

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Non-empirical calculations of the first ionization potential of silatranes and the electronic structure of their radical cations

Cited by 5 publications

References 12 publications

Assignment of photoelectron spectra of silatranes: first ionization energies and the nature of the dative Si←N contact

Assignment of photoelectron spectra of silatranes: first ionization energies and the nature of the dative Si←N contact

Molecular precursors of mesostructured silica materials in the atrane route: A DFT/GIAO/NBO theoretical study

Silatranes: a review on their synthesis, structure, reactivity and applications

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