IR Spectrum and Structure of a Protonated Disilane: Probing the SiHSi Proton Bridge

Savoca, Marco; Langer, Judith; Dopfer, Otto

doi:10.1002/anie.201208958

Cited by 36 publications

(38 citation statements)

References 48 publications

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“…Hydrogen termination is an effective means of passivation and stabilization of silicon clusters. [12][13][14][15][16][17] There is also significant interest in SiO 2 matrices with embedded nanocrystalline silicon. [18][19][20] For small isolated Si n clusters, dissociative adsorption of dioxygen molecules has a significant impact on their geometry and electronic structure.…”

Section: Introductionmentioning

confidence: 99%

Vibrational spectra and structures of bare and Xe-tagged cationic SinOm+ clusters

Savoca

Langer

Harding

et al. 2014

The Journal of Chemical Physics

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Vibrational spectra of Xe-tagged cationic silicon oxide clusters Si(n)O(m)(+) with n = 3-5 and m = n, n ± 1 in the gas phase are obtained by resonant infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory calculations. The Si(n)O(m)(+) clusters are produced in a laser vaporization ion source and Xe complexes are formed after thermalization to 100 K. The clusters are subsequently irradiated with tunable light from an IR free electron laser and changes in the mass distribution yield size-specific IR spectra. The measured IRMPD spectra are compared to calculated linear IR absorption spectra leading to structural assignments. For several clusters, Xe complexation alters the energetic order of the Si(n)O(m)(+) isomers. Common structural motifs include the Si2O2 rhombus, the Si3O2 pentagon, and the Si3O3 hexagon.

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Section: Introductionmentioning

confidence: 99%

Vibrational spectra and structures of bare and Xe-tagged cationic SinOm+ clusters

Savoca

Langer

Harding

et al. 2014

The Journal of Chemical Physics

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“…For this purpose, the octopole is filled with N 2 up to 10 À5 mbar, resulting in collisions with B10 eV collision energy in the laboratory frame. Recent applications of this IRPD approach of tagged ions in the Berlin laboratory include hydrocarbon ions, [48][49][50][51][52][53][54][55][56][57] silicon-containing ions, [58][59][60] and biological molecules and their hydrates. [61][62][63][64][65][66] 2.3.2.…”

Section: Experimental Methods For the Neutral Ai Moleculesmentioning

confidence: 99%

Diastereo-specific conformational properties of neutral, protonated and radical cation forms of (1R,2S)-cis- and (1R,2R)-trans-amino-indanol by gas phase spectroscopy

Bouchet

Klyne

Piani

et al. 2015

Phys. Chem. Chem. Phys.

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Chirality effects on the intramolecular interactions strongly depend on the charge and protonation states. Here, the influence of chirality on the structure of the neutral, protonated, and radical cation forms of (1R,2S)-cis-and (1R,2R)-trans-1-amino-2-indanol diastereomers, prototypical molecules with two chiral centers, is investigated in a molecular beam by laser spectroscopy coupled with quantum chemical calculations. The neutral systems are structurally characterised by double resonance IR-UV spectroscopy, while IR-induced dissociation spectroscopy is employed for the charged molecules. The sterical constraints due to the cyclic nature of the molecule emphasise the chirality effects, which manifest themselves by the formation of an intramolecular hydrogen bond in neutral or protonated (1R,2S)-cis-amino-indanol. In contrast, this interaction is not possible in (1R,2R)-trans-amino-indanol. In the protonated species, chirality also influences the spectroscopic probes in the NH/OH stretch range by fine-tuning subtle effects such as the hyperconjugation between the s(OH) orbital and s* orbitals localised on the alicyclic ring. The radical cation undergoes opening of the alicyclic ring, which results in an ionisation-induced loss of the chirality effects.

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“…15,16 Tagging with weakly-bound Rg atoms lowers the temperature of the ions and the effective dissociation energy. [17][18][19][20][21][22][23][24][25][26][27] This approach allows for recording single-photon IRPD spectra of cold ions, yielding higher spectral resolution and thus substantial improvement in the quality of the conformer assignment. Here, we apply this technique to determine the most stable conformers of ortho-fluorinated protonated PEA (oF-H + PEA), by analyzing the IRPD spectra of cold oF-H + PEA-Rg dimers with Rg = Ne and Ar in the NH stretch range.…”

Section: Introductionmentioning

confidence: 99%

Infrared spectrum of the cold ortho-fluorinated protonated neurotransmitter 2-phenylethylamine: competition between NH⁺⋯π and NH⁺⋯F interactions

Schütz

Bouchet

Dopfer

2016

Phys. Chem. Chem. Phys.

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Halogenation of pharmaceutical molecules is a common tool to modify their physiological properties. The geometric, vibrational, and electronic properties of the ortho-fluorinated protonated neurotransmitter 2-phenylethylamine (oF-HPEA) are characterized by infrared photodissociation (IRPD) spectroscopy in the NH stretch range using the messenger technique and dispersion-corrected density functional theory calculations at the B3LYP-D3/aug-cc-pVTZ level to elucidate the drastic effect of site-specific ortho-fluorination. The IRPD spectra of cold oF-HPEA-Rg dimers (Rg = Ne, Ar) are assigned to the most stable gauche conformer (Gf1) of oF-HPEA, which benefits from both NHπ and NHF interactions. A minor contribution (∼5%) of the slightly less stable Gf2 gauche conformer (E = +1.1 kJ mol) is also identified. Comparison of oF-HPEA with unsubstituted HPEA reveals a much stronger NHπ interaction in HPEA resulting in a large red shift of the bonded NH stretch frequency. This behavior is confirmed by natural bond orbital (NBO) analysis and noncovalent interaction (NCI) calculations. The Rg ligand prefers a binding site at which it can maximize the interaction with the aromatic π electron system and the ammonium group. Although the intermolecular interactions with the Rg atoms can compete with the noncovalent intramolecular bonds, they induce only minor spectral shifts in the NH stretch range.

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IR Spectrum and Structure of a Protonated Disilane: Probing the SiHSi Proton Bridge

Cited by 36 publications

References 48 publications

Vibrational spectra and structures of bare and Xe-tagged cationic SinOm+ clusters

Vibrational spectra and structures of bare and Xe-tagged cationic SinOm+ clusters

Diastereo-specific conformational properties of neutral, protonated and radical cation forms of (1R,2S)-cis- and (1R,2R)-trans-amino-indanol by gas phase spectroscopy

Infrared spectrum of the cold ortho-fluorinated protonated neurotransmitter 2-phenylethylamine: competition between NH⁺⋯π and NH⁺⋯F interactions

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IR Spectrum and Structure of a Protonated Disilane: Probing the SiHSi Proton Bridge

Cited by 36 publications

References 48 publications

Vibrational spectra and structures of bare and Xe-tagged cationic SinOm+ clusters

Vibrational spectra and structures of bare and Xe-tagged cationic SinOm+ clusters

Diastereo-specific conformational properties of neutral, protonated and radical cation forms of (1R,2S)-cis- and (1R,2R)-trans-amino-indanol by gas phase spectroscopy

Infrared spectrum of the cold ortho-fluorinated protonated neurotransmitter 2-phenylethylamine: competition between NH+⋯π and NH+⋯F interactions

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Infrared spectrum of the cold ortho-fluorinated protonated neurotransmitter 2-phenylethylamine: competition between NH⁺⋯π and NH⁺⋯F interactions