Wybren Jan Buma Molecular Photonics van ‘t Hoff Institute for Molecular Sciences University of Amsterdam Mechanically interlocked molecules in the gas phase: isolated molecule spectroscopy and dynamics MolMolPhotPhot EE SS

MolMolPhotPhot EE SS Mechanically interlocked molecules Two separate components Non-covalently bound macrocycle * macrocycle threadbinding site * thread → binding site Two separate components Non-covalently bound macrocycle * macrocycle threadbinding site * thread → binding site

MolMolPhotPhot EE SS Mechanically interlocked molecules Weak bond provides unique rotationaltranslational rotational and translational degrees of freedom controllablereversible that can be accessed in a controllable and reversible manner Weak bond provides unique rotationaltranslational rotational and translational degrees of freedom controllablereversible that can be accessed in a controllable and reversible manner

MolMolPhotPhot EE SSObjectives To control and manipulate molecular motors requires conformational landscape * exploration of conformational landscape interactions * knowledge of interactions between the interlocked parts relative movement * characterization relative movement To control and manipulate molecular motors requires conformational landscape * exploration of conformational landscape interactions * knowledge of interactions between the interlocked parts relative movement * characterization relative movement

MolMolPhotPhot EE SS Gas phase experiments isolate * isolate molecules from external effects (solvent) * heating induces changes or decomposition laser desorption * laser desorption technique to vaporize them supersonic expansion * cool molecules by entraining them into supersonic expansion isolate * isolate molecules from external effects (solvent) * heating induces changes or decomposition laser desorption * laser desorption technique to vaporize them supersonic expansion * cool molecules by entraining them into supersonic expansion

MolMolPhotPhot EE SS High-resolution spectroscopy Laser desorption Mass spectrum Excitation spectrum IR absorption spectrum + supersonic beam

MolMolPhotPhot EE SSSpectroscopy supersonic beam desorption laser sample nozzle ions Excitation & ionization laser detector 1064 nm

MolMolPhotPhot EE SS Multiphoton ionization spectroscopy Mass-selected vibrationally-resolved excitation spectra S0S0 S1S1 IE Excitation energy + ion

MolMolPhotPhot EE SS IR ion dip spectroscopy ~ 200 ns IR UV S 0 v=0 S1S1 IE S 0 v=1 + ion detection NH NH stretch frequencies diagnostic of details (changes in)hydrogen-bonding 10 Ion signal

MolMolPhotPhot EE SS Does it work ? macrocycle rotaxane 1148 amu

MolMolPhotPhot EE SS Problems to be tackled today I.How does the macrocycle effect the conformational phase space conformational phase space of the thread ? interactions II.Can we characterise the interactions between macrocycle and thread and find signatures for them ? I.How does the macrocycle effect the conformational phase space conformational phase space of the thread ? interactions II.Can we characterise the interactions between macrocycle and thread and find signatures for them ?

MolMolPhotPhot EE SS Building blocks in the gas phase

MolMolPhotPhot EE SS Excitation spectrum thread origin 6b a 0 1 6b b

MolMolPhotPhot EE SS Excitation spectrum thread

MolMolPhotPhot EE SS Low-frequency vibrations thread FFT 49 cm cm -1

MolMolPhotPhot EE SS Cooling conditions xenon argon ~30 cm -1 ~12 cm -1

MolMolPhotPhot EE SS Molecular motors in the gas phase 193 nm ionization

MolMolPhotPhot EE SS Molecular motors in the gas phase ~30 cm -1 ~10 cm -1 Direct view on conformational phase space restriction conformational phase space restriction by macrocycle

MolMolPhotPhot EE SS Mechanically interlocked molecules

MolMolPhotPhot EE SS REMPI excitation spectroscopy: macrocycle

MolMolPhotPhot EE SS Ion-dip spectroscopy: macrocycle C-HN-H

MolMolPhotPhot EE SS Ion-dip spectroscopy: rotaxane

MolMolPhotPhot EE SS NH..... O=C NH thread Ion-dip spectroscopy: rotaxane NH macrocycle

MolMolPhotPhot EE SS Present experiments IR-UV hole-burning spectroscopy at Free Electron Laser for Infrared eXperiments Free Electron Laser for Infrared eXperiments (FELIX) (C=O, fingerprint region) Far IR ( cm -1 ) (C=O, fingerprint region) brings within reach: - detailed view on conformational landscape - vibrations of macrocycle with respect to the thread (< 400 cm-1) IR-UV hole-burning spectroscopy at Free Electron Laser for Infrared eXperiments Free Electron Laser for Infrared eXperiments (FELIX) (C=O, fingerprint region) Far IR ( cm -1 ) (C=O, fingerprint region) brings within reach: - detailed view on conformational landscape - vibrations of macrocycle with respect to the thread (< 400 cm-1)

MolMolPhotPhot EE SSConclusions We can bring supramolecular assemblies in the gas phase and perform high-resolution spectroscopy  Influence of macrocycle on conformational phase space thread  Conformational flexibility available to assembly We can bring supramolecular assemblies in the gas phase and perform high-resolution spectroscopy  Influence of macrocycle on conformational phase space thread  Conformational flexibility available to assembly

MolMolPhotPhot EE SS UvA Anouk Rijs Dick Bebelaar UC Santa Barbara Ali Abu-Riziq Bridgit Crews Mattanjah de Vries University of Edinburgh David LeighUvA Anouk Rijs Dick Bebelaar UC Santa Barbara Ali Abu-Riziq Bridgit Crews Mattanjah de Vries University of Edinburgh David Leigh Funding NWO EC-TMR (RTN) EC-FET EC-NMP EC-Marie Curie