Optical investigation of the Si-H bond and peculiarities in its chemical behavior in various compounds

Batuev, M. I.; Petrov, A. D.; Пономаренко, В. А.; Matveeva, A. D.

doi:10.1007/bf01173786

Cited by 5 publications

(5 citation statements)

References 4 publications

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“…Figure shows FTIR spectra of the Si–H vibrational mode (ν Si–H ) for the unreacted TriMOS precursor (ν Si–H = 2197 cm –1 ) dissolved in isopropanol and grafted to the four different MSNPs suspended in isopropanol. The silane vibrational frequency reports on the level of condensation within the silica matrix through the inductive effect. − In this study, the silica particles were fully formed at the time of grafting, so any differences in ν Si–H are due to the degree of condensation of TriMOS on the nanoparticle surface. The blue-shifted Si–H peaks in Figure illustrate the success of the TriMOS grafting technique, which, to our knowledge, is the first report of grafting of Si–H groups to a silica nanoparticle surface.…”

Section: Resultsmentioning

confidence: 85%

2D-IR Spectroscopy of Porous Silica Nanoparticles: Measuring the Distance Sensitivity of Spectral Diffusion

et al. 2015

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Two-dimensional infrared spectroscopy (2D-IR) was used to investigate the sensitivity of a vibrational mode to spectral diffusion on the nanometer length scale. A confined volume within a porous silica nanoparticle was used as the model system. Utilizing a novel grafting technique, silane probes were covalently secured to the pore surface for a series of templated mesoporous silica nanoparticles with variable pore sizes. 2D-IR measurements determined that isopropanol exhibited two dominant time scales of ultrafast motions within the pores with time scales of a few picoseconds and tens of picoseconds. The unique perspective of the probe on a surface revealed that the vibrational dynamics of the reporting mode were perturbed by molecules up to ∼5 nm away. The data were modeled well by a 1/d 2 distance dependence for the coupling of solvent dynamics to frequency fluctuations and a logistic radial distribution of fast and slow dynamic populations.

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Section: Resultsmentioning

confidence: 85%

2D-IR Spectroscopy of Porous Silica Nanoparticles: Measuring the Distance Sensitivity of Spectral Diffusion

et al. 2015

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“…In order to be an effective solvation probe, the solvent accessible silane vibrations also need to be spectroscopically sensitive to different solvents. For small molecule silanes, the Si–H vibrational frequency has been shown to be dependent on the inductive effect of the other three substituents. − Smith and co-workers have constructed a model that shows correlation between the sum of the electronegativity of the nearest neighbors and Si–H frequency . That model subsequently incorporates the contribution of next nearest neighbors as the second term in a series; however, this second term showed little to no influence on ν Si–H .…”

Section: Resultsmentioning

confidence: 99%

Characterizing Solvent Dynamics in Nanoscopic Silica Sol–Gel Glass Pores by 2D-IR Spectroscopy of an Intrinsic Vibrational Probe

Huber

Massari

2014

J. Phys. Chem. C

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Porous sol–gel matrices were synthesized with IR-active Si–H vibrational chromophores integrated into the silica network. The Si–H vibrational mode was found to be highly accessible to solvents within the nanoscopic pores. Vibrational solvatochromism of the silane vibration was controlled largely by interactions between infiltrating solvents and the oxygen and hydroxide sites in the silica. Exchanging solvents in the silica matrices produced reversible solvatochromic shifts in some cases but led to irreversible shifts when strongly interacting solvents were tested, suggesting that a layer of solvent was not exchangeable. 2D-IR spectroscopy was used to monitor spectral diffusion and extract the homogeneous line widths of the Si–H mode for a range of infiltrating solvents as well as solvent-free aerogel samples. It was demonstrated that the silane vibration is sensitive to the nature of the infiltrating solvent, making these vibrationally active sol–gel films a general platform for solvent dynamics in nanoscopic confined volumes.

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“…It has been established that ν Si-H is tuned by the inductive effect of the substituents. [66][67][68][69][70] A major difference between TriMOS and TriPS is the presence of electronegative oxygen atoms in the methoxy ligands that strongly polarize the Si-O bonds; the partial atomic charge on silicon changes from 0.08 e in TriPS to 1.03 e in TriMOS (Table SI of the supplementary material). Previous analysis showed that the hydrogen bonding ability of the solvent was correlated with solvatochromic shifts of ν Si-H on silanes and silica sol-gels.…”

Section: Experimental Methodsmentioning

confidence: 99%

Enhanced vibrational solvatochromism and spectral diffusion by electron rich substituents on small molecule silanes

Olson

Grofe

Huber

et al. 2017

The Journal of Chemical Physics

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Fourier transform infrared and two-dimensional IR (2D-IR) spectroscopies were applied to two different silanes in three different solvents. The selected solutes exhibit different degrees of vibrational solvatochromism for the Si-H vibration. Density functional theory calculations confirm that this difference in sensitivity is the result of higher mode polarization with more electron withdrawing ligands. This mode sensitivity also affects the extent of spectral diffusion experienced by the silane vibration, offering a potential route to simultaneously optimize the sensitivity of vibrational probes in both steady-state and time-resolved measurements. Frequency-frequency correlation functions obtained by 2D-IR show that both solutes experience dynamics on similar time scales and are consistent with a picture in which weakly interacting solvents produce faster, more homogeneous fluctuations. Molecular dynamics simulations confirm that the frequency-frequency correlation function obtained by 2D-IR is sensitive to the presence of hydrogen bonding dynamics in the surrounding solvation shell.

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Optical investigation of the Si-H bond and peculiarities in its chemical behavior in various compounds

Cited by 5 publications

References 4 publications

2D-IR Spectroscopy of Porous Silica Nanoparticles: Measuring the Distance Sensitivity of Spectral Diffusion

2D-IR Spectroscopy of Porous Silica Nanoparticles: Measuring the Distance Sensitivity of Spectral Diffusion

Characterizing Solvent Dynamics in Nanoscopic Silica Sol–Gel Glass Pores by 2D-IR Spectroscopy of an Intrinsic Vibrational Probe

Enhanced vibrational solvatochromism and spectral diffusion by electron rich substituents on small molecule silanes

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