Metal exchange in the field desorption mass spectra of some transition metal metal crown ether complexes. Surface effects

Henis, Neil B.H.; Fraley, David F.; Bursey, Maurice M.

doi:10.1016/0020-1650(81)80041-4

Cited by 10 publications

(3 citation statements)

References 13 publications

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“…The spectral data suggested the existence of a CoCl 4 2– counteranion in the solid product, but no information was obtained for the cationic (Co 2+ –CE) part . Subsequently, a number of papers have reported CE complexes with transition-metal ions in the condensed phase and the gas phase. − Concerning spectroscopy of divalent transition-metal ion–CE complexes in the gas phase, Rodriguez and Lisy reported IR predissociation spectroscopy of Mn 2+ (18-crown-6)(CH 3 OH) n ( n = 1–3) complexes in the CH and OH stretching regions . In the n = 2 and 3 complexes, a CH 3 OH···CH 3 OH intermolecular bond is formed, providing intense hydrogen-bonded OH stretching bands.…”

Section: Introductionmentioning

confidence: 99%

UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn²⁺(benzo-15-crown-5)(H₂O)_0–2

2019

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Ultraviolet photodissociation (UVPD) and IR–UV double-resonance spectroscopy are performed for bare and microhydrated complexes of Mn2+(benzo-15-crown-5), Mn2+(B15C5)(H2O) n (n = 0–2), under cold (∼10 K) gas-phase conditions. Density functional theory (DFT) calculations are also carried out to derive information on the geometric and electronic structures of the complexes from the experimental results. The n = 0 complex shows broad features in the UVPD spectrum, whereas the UV spectra of the n = 1 and 2 complexes exhibit sharp vibronic bands. The IR–UV and DFT results suggest that there is only one isomer each for the n = 1 and 2 complexes in which H2O molecules are directly attached to the Mn2+ ion through Mn2+···OH2 bonds with no intermolecular bond between the water molecules. Time-dependent DFT calculations suggest that the π–π* transition of the B15C5 part is highly mixed with the “ligand to metal charge transfer” transition in the n = 0 complex, which can result in broad features in the UVPD spectrum. In contrast, attachment of H2O molecules to Mn2+(B15C5) suppresses the mixing, providing sharp vibronic bands assignable to the π–π* transition for the n = 1 and 2 complexes. These results indicate that the electronic structure and transition of benzo-crown ether complexes with transition metals are strongly affected by solvation.

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Section: Introductionmentioning

confidence: 99%

UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn²⁺(benzo-15-crown-5)(H₂O)_0–2

2019

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“…Subsequently, there have been a number of reports on CE complexes with transition metal ions in the condensed phase and gas phase. 4−18 In these studies, the formation and geometric structures of the CE complexes were examined by X-ray diffraction, 9,10,14,15 IR spectroscopy, 5,7,11,12,15,17,18 NMR spectroscopy, 6,7,11 mass spectrometry, 13,16 and thermochemical measurements. 4,8 Very few studies discussed the coordination of macromolecules to the transition metal ions on the basis of absorption of the transition metal ions in the visible and near-IR regions.…”

Section: Introductionmentioning

confidence: 99%

“…This implies that the complex formation of CEs with Ag + can strongly affect the electronic structure of the CE moiety. Subsequently, there have been a number of reports on CE complexes with transition metal ions in the condensed phase and gas phase. − In these studies, the formation and geometric structures of the CE complexes were examined by X-ray diffraction, ,,, IR spectroscopy, ,,,,,, NMR spectroscopy, ,, mass spectrometry, , and thermochemical measurements. , Very few studies discussed the coordination of macromolecules to the transition metal ions on the basis of absorption of the transition metal ions in the visible and near-IR regions. , Concerning spectroscopy of transition metal ion–CE complexes in the gas phase, Rodriguez and Lisy reported IR predissociation spectroscopy of Mn 2+ (18-crown-6)(CH 3 OH) n ( n = 1–3) complexes in the CH and OH stretching regions . Cooper et al studied the IR multiple photon spectra of Zn 2+ and Cd 2+ complexes with CEs using a free electron laser .…”

Section: Introductionmentioning

confidence: 99%

Geometric and Electronic Structures of Ag⁺(benzo-18-crown-6), Ag⁺(dibenzo-18-crown-6), and Ag⁺(dibenzo-15-crown-5) Complexes Investigated by Cold Gas-Phase Spectroscopy

et al. 2019

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The UV photodissociation (UVPD) spectra of Ag + complexes with benzo-18-crown-6 (B18C6), dibenzo-18crown-6 (DB18C6), and dibenzo-15-crown-5 (DB15C5) [Ag + (B18C6), Ag + (DB18C6), and Ag + (DB15C5)] are observed under cold gas-phase conditions. Ag + (B18C6) and Ag + (DB18C6) show sharp vibronic bands in the 36000− 37200 cm − 1 region, while the UVPD spectrum of Ag + (DB15C5) is very broad. These UV bands are assigned to the π−π* transition, which is localized on the B18C6, DB18C6, and DB15C5 part of the complexes. Quantum chemical calculations suggest that the broad UV feature of Ag + (DB15C5) can be attributed to the short lifetimes of optically excited ππ* states due to internal conversion (IC) to low-lying excited states that are present only for this complex. The appearance of the π−π* transition in the same UV region as that of the neutral crown ethers and their complexes with alkali metal ions indicates that the positive charge is localized on the Ag atom in these complexes. However, the fragment ions produced after UV absorption are B18C6 + , DB18C6 + , and DB15C5 + radical ions, indicating that they are produced via charge transfer (CT) between the Ag + ion and benzo-crown ethers. The CT during fragmentation is attributed to the higher ionization energy of Ag atom when compared to the benzo-crown ethers. In the complexes, the Ag + ion is effectively encapsulated by the crown cavity of the benzo-crown ethers without transferring the positive charge from Ag + to the crown. However, UV excitation of the Ag + (B18C6), Ag + (DB18C6), and Ag + (DB15C5) complexes can reduce the Ag + ion and produce a Ag atom with high efficiency in the gas phase.

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Fractionation of alkali metal cations in cationization of phthalic acid. A fast atom bombardment study

Bursey

Marbury

Hass

1984

Biol. Mass Spectrom.

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Metal exchange in the field desorption mass spectra of some transition metal metal crown ether complexes. Surface effects

Cited by 10 publications

References 13 publications

UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn²⁺(benzo-15-crown-5)(H₂O)_0–2

UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn²⁺(benzo-15-crown-5)(H₂O)_0–2

Geometric and Electronic Structures of Ag⁺(benzo-18-crown-6), Ag⁺(dibenzo-18-crown-6), and Ag⁺(dibenzo-15-crown-5) Complexes Investigated by Cold Gas-Phase Spectroscopy

Fractionation of alkali metal cations in cationization of phthalic acid. A fast atom bombardment study

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Metal exchange in the field desorption mass spectra of some transition metal metal crown ether complexes. Surface effects

Cited by 10 publications

References 13 publications

UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn2+(benzo-15-crown-5)(H2O)0–2

UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn2+(benzo-15-crown-5)(H2O)0–2

Geometric and Electronic Structures of Ag+(benzo-18-crown-6), Ag+(dibenzo-18-crown-6), and Ag+(dibenzo-15-crown-5) Complexes Investigated by Cold Gas-Phase Spectroscopy

Fractionation of alkali metal cations in cationization of phthalic acid. A fast atom bombardment study

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UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn²⁺(benzo-15-crown-5)(H₂O)_0–2

UV and IR Spectroscopy of Transition Metal–Crown Ether Complexes in the Gas Phase: Mn²⁺(benzo-15-crown-5)(H₂O)_0–2

Geometric and Electronic Structures of Ag⁺(benzo-18-crown-6), Ag⁺(dibenzo-18-crown-6), and Ag⁺(dibenzo-15-crown-5) Complexes Investigated by Cold Gas-Phase Spectroscopy