Dispersion interactions are omnipresent in intermolecular interactions, but their respective contributions are difficult to predict. Aromatic ethers offer competing docking sites for alcohols: the ether oxygen as a well known hydrogen bond acceptor, but also the aromatic π system. The interaction with two aromatic moieties in diphenyl ether can tip the balance towards π binding. We use a multi-spectroscopic approach to study the molecular recognition, the structure and internal dynamics of the diphenyl ether-methanol complex, employing infrared, infrared-ultraviolet and microwave spectroscopy. We find that the conformer with the hydroxy group of the alcohol binding to one aromatic π cloud and being coordinated by an aromatic C-H bond of the other phenyl group is preferred. Depending on the expansion conditions in the supersonic jet, we observe a second conformer, which exhibits a hydrogen bond to the ether oxygen and is higher in energy.

a Aromatic ethers such as diphenyl ether (DPE) represent molecules with different docking sites for alcohols leading to competing OH-O and OH-p interactions. In a multi-spectroscopic approach in combination with quantum chemical calculations the complex of DPE with tert-butyl alcohol (t-BuOH) is investigated in the electronic ground state (S 0 ) and the electronically excited state (S 1 ). FTIR, microwave as well as mass-and isomer-selective IR/R2PI spectra are recorded, revealing co-existing OH-O and OH-p isomers in the S 0 state. Surprisingly, they are predicted to be of almost equal stability in contrast to the previously investigated DPE-MeOH complex, where the OH-p structure is preferred by both theory and experiment. The tert-butyl group in t-BuOH allows for a simultaneous optimization of hydrogen-bonding and dispersion interactions, which provides a sensitive meeting point between theory and experiment. In the electronically excited state of DPE-t-BuOH, vibrational spectra could be recorded separately for both isomers using UV/IR/UV spectroscopy. In the S 1 state the same structural binding motifs are obtained as in the S 0 state with the OH-O bond being weakened for the OH-O arrangement and the OH-p interaction being strengthened in the case of the OH-p isomer compared to the S 0 state.

The planarity and rigidity of dibenzofuran inverts the docking preference for increasingly bulky R-OH solvent molecules, compared to the closely related diphenyl ether. Now, London dispersion favors OH⋯π hydrogen bonding.

Dispersion interactions can play an important role in understanding unusual binding behaviors. This is illustrated by a systematic study of the structural preferences of diphenyl ether (DPE)-alcohol aggregates, for which OH⋅⋅⋅O-bound or OH⋅⋅⋅π-bound isomers can be formed. The investigation was performed through a multi-spectroscopic approach including IR/UV and microwave methods, combined with a detailed theoretical analysis. The resulting solvent-size-dependent trend for the structural preference turns out to be counter-intuitive: the hydrogen-bonded OH⋅⋅⋅O structures become more stable for larger alcohols, which are expected to be stronger dispersion energy donors and thus should prefer an OH⋅⋅⋅π arrangement. Dispersion interactions in combination with the twisting of the ether upon solvent aggregation are key for understanding this preference.

Diphenyl ether offers competing docking sites for methanol: the ether oxygen acts as a common hydrogen-bond acceptor and the π system of each phenyl ring allows for OH-π interactions driven by electrostatic, induction, and dispersion forces. Based on investigations in the electronic ground state (S ), we present a detailed study of the electronically excited state (S ) and the ionic ground state (D ), in which an impact on the structural preference is expected compared with the S state. Dispersion forces in the electronically excited state were analyzed by comparing the computed binding energies at the coupled-cluster-singles (CCS) and approximate coupled-cluster-singles-doubles levels of theory (CC2 approximation). By applying UV/IR/UV spectroscopy, we found a more strongly bound OH-π structure in the S state compared with the S state, in agreement with spin-component-scaled CC2 calculations. A structural rearrangement into a non-hydrogen-bonded structure takes places upon ionization in the D state, which was revealed by using IR photodissociation spectroscopy and confirmed by theory.

The structure of the isolated aggregate of phenyl vinyl ether and methanol is studied by combining a multi-spectroscopic approach and quantum-chemical calculations in order to investigate the delicate interplay of noncovalent interactions. The complementary results of vibrational and rotational spectroscopy applied in molecular beam experiments reveal the preference of a hydrogen bond of the methanol towards the ether oxygen (OH∙∙∙O) over the π-docking motifs via the phenyl and vinyl moieties, with an additional less populated OH∙∙∙P(phenyl)-bound isomer detected only by microwave spectroscopy. The correct prediction of the energetic order of the isomers using quantum-chemical calculations turns out to be challenging and succeeds with a sophisticated local coupled cluster method. The latter also yields a quantification as well as a visualization of London dispersion, which prove to be valuable tools for understanding the role of dispersion on the docking preferences. Beyond the structural analysis of the electronic ground state (S0), the electronically excited (S1) state is analyzed, in which a destabilization of the OH∙∙∙O structure compared to the S0 state is observed experimentally and theoretically.

In this paper we present the first investigations on an isolated linear depsipetide CyCO-Gly-Lac-NH-PhOMe (cyclohexylcarbonyl-glycine-lactate-2-anisidine abbreviated as MOC) in a molecular beam experiment. Depsipeptides are a special subclass of peptides which contain at least one ester bond replacing a peptide bond. This leads to a different folding behavior and a different biological activity compared to a "normal" peptide. In order to analyze the folding of an isolated depsipeptide on a molecular level a variety of combined IR/UV methods including IR/IR/UV experiments are applied to MOC. Three different isomers are identified in combination with DFT calculations using the hybrid functional B3LYP-D3 with a TZVP basis set. The most stable structure shows a tweezer-like arrangement between the aromatic chromophore and the aliphatic cyclohexyl ring. A characteristic feature of this structure is that it is stabilized by dispersion interactions resulting from CH/π interactions. If dispersion is not taken into account this structural arrangement is no longer a minimum on the potential energy surface indicating the importance of dispersion interactions.

We report on a detailed multi-spectroscopic analysis of the structures and internal dynamics of diphenylether and its aggregates with up to three water molecules by employing molecular beam experiments.