Structural Rearrangement by Isomer-Specific Infrared Excitation in the Neutral Isolated Dihydrated Cluster of 3-Hydroxyflavone.

Isomer-specific, IR-induced reactions in the electronic ground state (S0) can be of great interest to control reaction pathways. Here we show a first example of these reactions with isomer-specific excitation and formation of a new isomer under isolated conditions in a molecular beam experiment. The investigated dihydrated cluster of 3-hydroxyflavone forms two isomers, I and D, in the S0 state. We show that only a mode-specific excitation of isomer I leads to a structural rearrangement yielding an isomer that has not been identified so far. This isomer is assigned in comparison to quantum chemical calculations. The experiments are performed by applying an IR/IR method in combination with a mass-selective resonant two-photon ionization (R2PI) process. Usually these kinds of IR/IR/R2PI methods are chosen to discriminate isomers; here it is demonstrated that this powerful method can also be applied for analysis of IR-induced reactions probed by an IR/R2PI process.

The Structure of Diphenyl Ether-Methanol in the Electronically Excited and Ionic Ground States: A Combined IR/UV Spectroscopic and Theoretical Study.

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 (S0 ), we present a detailed study of the electronically excited state (S1 ) and the ionic ground state (D0 ), in which an impact on the structural preference is expected compared with the S0 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 S1 state compared with the S0 state, in agreement with spin-component-scaled CC2 calculations. A structural rearrangement into a non-hydrogen-bonded structure takes places upon ionization in the D0 state, which was revealed by using IR photodissociation spectroscopy and confirmed by theory.

Aromatic embedding wins over classical hydrogen bonding - a multi-spectroscopic approach for the diphenyl ether-methanol complex.

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.

ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

Adaptive aggregation of peptide model systems.

Jet-cooled infrared spectra of acetylated glycine, alanine, and dialanine esters and their dimers are reported in the amide A and amide I-III regions. They serve as particularly simple peptide aggregation models and are found to prefer a single backbone conformation in the dimer that is different from the most stable monomer backbone conformation. In the case of alanine, evidence for topology-changing chirality discrimination upon dimer formation is found. The jet spectroscopic results are compared to gas phase spectra and quantum chemical calculations. They provide reliable benchmarks for the evaluation of the latter in the field of peptide interactions.