Imaging the Solvation of a One‐Dimensional Solid on the Molecular Scale

Lucht, Karsten; Trosien, Iris; Sander, Wolfram; Morgenstern, Karina

doi:10.1002/anie.201808579

Cited by 22 publications

(34 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The question of whether microsolvation can explain macrosolvation remains controversial. , While bulk solvent effects can be determined using standard spectroscopy in solution, specific solvation is experimentally challenging because well-defined solvent–solute complexes have to be characterized. − Such solvent–solute complexes can be synthesized and spectroscopically characterized in cryogenic matrices which provides a method to differentiate the effects of micro- and macrosolvation. Microsolvation can be studied by probing the interaction of isolated solute molecules with a small number of explicit solvent molecules in an apolar rare gas matrix that mimics gas-phase conditions.…”

Section: Introductionmentioning

confidence: 99%

Micro- vs Macrosolvation in Reichardt’s Dyes

2021

Self Cite

View full text Add to dashboard Cite

Solvation is a complex phenomenon involving electrostatic and van der Waals forces as well as chemically more specific effects such as hydrogen bonding. To disentangle global solvent effects (macrosolvation) from local solvent effects (microsolvation), we studied the UV−vis and IR spectra of a solvatochromic pyridinium-N-phenolate dye (a derivative of Reichardt's dye) in rare gas matrices, in mixtures of argon and water, and in water ice. The π−π* transition of the betaine dye in the visible region and its C−O stretching vibration in the IR region are highly sensitive to solvent effects. By annealing argon matrices of the betaine dye doped with low concentrations of water, we were able to synthesize 1:1 water−dye complexes. Formation of hydrogen-bonded complexes leads to small shifts of the π−π* transition only, as long as the global polarity of the matrix environment does not change. In contrast, changes of the global polarity result in large spectral band shifts. Hydrogen-bonded complexes of the betaine dye are more sensitive to global polarity changes than the dye itself, explaining why E T values determined with Reichardt's dyes are very different for protic and nonprotic solvents, even if the relative permittivities of these solvents are similar.

show abstract

Section: Introductionmentioning

confidence: 99%

Micro- vs Macrosolvation in Reichardt’s Dyes

2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…The two conformers are expected to be close in energy but separated by an activation barrier of several kcal mol −1 , depending on the substituents in 9‐position, which should inhibit the thermal interconversion of the conformers at cryogenic temperatures. The IR spectra of precursor 5 obtained after vapor deposition with a large excess of argon on a cold spectroscopic window reveal that the gas phase equilibrium of 5 ‐ d : 5 ‐ u of approximately 3:2 is efficiently trapped in the matrix (Supporting Information, Figure S1 and Table S2) . A thermal interconversion between 5 ‐ u and 5 ‐ d is not observed during annealing of these matrices at temperatures up to 35 K.…”

Section: Methodsmentioning

confidence: 99%

Conformational Spin Switching and Spin‐Selective Hydrogenation of a Magnetically Bistable Carbene

et al. 2019

Self Cite

View full text Add to dashboard Cite

The control of the spin states of molecules opens the path to tuning selectivity in chemicalr eactions and to developing novel magnetically switchable materials.3-Methoxy-9fluorenylidene is ac arbene that is generated in cryogenic matrices both in its lowest energy singlet and triplet states,and the ratio of these states can be shifted by selective irradiation. The interconversion of the nearly degenerate spin states is induced by ac onformational change of the methoxy group: switching the methoxy group into the "up" position results in the singlet state and switching into the "down" position in the triplet state.T he spin control via ar emote functional group makes this carbene unique for the study of spin-specific reactions,w hich is demonstrated for the hydrogenation reaction. Spin switching by switching the conformation of aremote functional group is an ovel phenomenon with potential applications in the design of functional materials.

show abstract

“…Such hydrogen bonds are crucial for the solvation processes in polar solvents, 7 in general, for example, for water from atomic ions 8,9 to larger particles. 10,11 As these two polar solvents, water and ammonia, are isoelectronic, their hydrogen-bonded dimer structures were frequently compared. The linear hydrogen bond in a water dimer is reflected in its higher binding energy of approximately 5.1 kcal/mol (225 meV) 12 compared to that of approximately 2.9 kcal/mol (130 meV) in an ammonia dimer, which is nonlinear, eclipsed, and quite flexible in the gas phase with the lowest energy at an angle of 17−20°.…”

Section: Introductionmentioning

confidence: 99%

“…Ammonia (NH 3 ) is a well known and important polar solvent, used both for electron solvation − and in organic chemistry due to its capability to form hydrogen bonds. Such hydrogen bonds are crucial for the solvation processes in polar solvents, in general, for example, for water from atomic ions , to larger particles. , …”

Section: Introductionmentioning

confidence: 99%

Influence of the Lattice Structure of Copper Surfaces on Ammonia Dimer Formation

2021

Self Cite

View full text Add to dashboard Cite

The restriction imposed by the lattice structure of different surfaces is used to investigate the influence of the distance between two monomers on their ability to bind to each other. We compare the interaction of ammonia monomers at two distinct distances imposed by the surface structure of a Cu(511) highindex surface to that of a Cu(110) low-index surface using lowtemperature scanning tunneling microscopy, inelastic tunneling spectroscopy, and density functional theory. Frustrated translational and rotational modes, the Mulliken and Bader charge analyses, and electrostatic potential mapping indicate chemisorption of ammonia monomers on both surfaces, with their dipoles oriented perpendicular to the surface plane. At a larger intermolecular distance of around 0.51 nm on step edges of Cu( 511), the monomers slightly repel each other due to electrostatic repulsion. At a shorter distance of around 0.36 nm perpendicular to the close-packed rows on Cu(110), a noticeable charge transfer between adjacent monomers indicates binding, that is, dimer formation in parallel orientation. This binding energy of the molecules compensates for the electrostatic repulsion. Our results outline how the choice of the surface structure may be utilized to alter the intermolecular interaction of solvent molecules and to enforce or suppress dimer formation.

show abstract

Imaging the Solvation of a One‐Dimensional Solid on the Molecular Scale

Cited by 22 publications

References 39 publications

Micro- vs Macrosolvation in Reichardt’s Dyes

Micro- vs Macrosolvation in Reichardt’s Dyes

Conformational Spin Switching and Spin‐Selective Hydrogenation of a Magnetically Bistable Carbene

Influence of the Lattice Structure of Copper Surfaces on Ammonia Dimer Formation

Contact Info

Product

Resources

About