TY - JOUR
A1 - Goulet-Hanssens, Alexis
A1 - Rietze, Clemens
A1 - Titov, Evgenii
A1 - Abdullahu, Leonora
A1 - Grubert, Lutz
A1 - Saalfrank, Peter
A1 - Hecht, Stefan
T1 - Hole Catalysis as a General Mechanism for Efficient and Wavelength-Independent Z -> E Azobenzene Isomerization
JF - CHEM
N2 - Whereas the reversible reduction of azobenzenes has been known for decades, their oxidation is destructive and as a result has been notoriously overlooked. Here, we show that a chain reaction leading to quantitative Z -> E isomerization can be initiated before reaching the destructive anodic peak potential. This hole-catalyzed pathway is accessible to all azobenzenes, without exception, and offers tremendous advantages over the recently reported reductive, radical-anionic pathway because it allows for convenient chemical initiation without the need for electrochemical setups and in the presence of air. In addition, catalytic amounts of metal-free sensitizers, such as methylene blue, can be used as excited-state electron acceptors, enabling a shift of the excitation wavelength to the far red of the azobenzene absorption (up to 660 nm) and providing quantum yields exceeding unity (up to 200%). Our approach will boost the efficiency and sensitivity of optically dense liquid-crystalline and solid photo-switchable materials.
Y1 - 2018
U6 - https://doi.org/10.1016/j.chempr.2018.06.002
SN - 2451-9294
VL - 4
IS - 7
SP - 1740
EP - 1755
PB - Cell Press
CY - Cambridge
ER -
TY - JOUR
A1 - Goulet-Hanssens, Alexis
A1 - Utecht, Manuel
A1 - Mutruc, Dragos
A1 - Titov, Evgenii
A1 - Schwarz, Jutta
A1 - Grubert, Lutz
A1 - Bleger, David
A1 - Saalfrank, Peter
A1 - Hecht, Stefan
T1 - Electrocatalytic Z -> E Isomerization of Azobenzenes
JF - Journal of the American Chemical Society
N2 - A variety of azobenzenes were synthesized to study the behavior of their E and Z isomers upon electrochemical reduction. Our results show that the radical anion of the Z isomer is able to rapidly isomerize to the corresponding E configured counterpart with a dramatically enhanced rate as compared to the neutral species. Due to a subsequent electron transfer from the formed E radical anion to the neutral Z starting material the overall transformation is catalytic in electrons; i.e., a substoichiometric amount of reduced species can isomerize the entire mixture. This pathway greatly increases the efficiency of (photo)switching while also allowing one to reach photostationary state compositions that are not restricted to the spectral separation of the individual azobenzene isomers and their quantum yields. In addition, activating this radical isomerization pathway with photoelectron transfer agents allows us to override the intrinsic properties of an azobenzene species by triggering the reverse isomerization direction (Z -> E) by the same wavelength of light, which normally triggers E -> Z isomerization. The behavior we report appears to be general, implying that the metastable isomer of a photoswitch can be isomerized to the more stable one catalytically upon reduction, permitting the optimization of azobenzene switching in new as well as indirect ways.
Y1 - 2017
U6 - https://doi.org/10.1021/jacs.6b10822
SN - 0002-7863
VL - 139
IS - 1
SP - 335
EP - 341
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Kasyanenko, Nina
A1 - Lysyakova, Liudmila
A1 - Ramazanov, Ruslan
A1 - Nesterenko, Alexey
A1 - Yaroshevich, Igor
A1 - Titov, Evgenii
A1 - Alexeev, G.
A1 - Lezov, Andrey
A1 - Unksov, I.
T1 - Conformational and Phase Transitions in DNA-Photosensitive Surfactant Solutions: Experiment and Modeling
JF - Biopolymers
N2 - DNA binding to trans- and cis-isomers of azobenzene containing cationic surfactant in 5 mM NaCl solution was investigated by the methods of dynamic light scattering (DLS), low-gradient viscometry (LGV), atomic force microscopy (AFM), circular dichroism (CD), gel electrophoresis (GE), flow birefringence (FB), UV-Vis spectrophotometry. Light-responsive conformational transitions of DNA in complex with photosensitive surfactant, changes in DNA optical anisotropy and persistent length, phase transition of DNA into nanoparticles induced by high surfactant concentration, as well as transformation of surfactant conformation under its binding to macromolecule were studied. Computer simulations of micelles formation for cis- and trans-isomers of azobenzene containing surfactant, as well as DNA-surfactant interaction, were carried out. Phase diagram for DNA-surfactant solutions was designed. The possibility to reverse the DNA packaging induced by surfactant binding with the dilution and light irradiation was shown. (c) 2014 Wiley Periodicals, Inc. Biopolymers 103: 109-122, 2015.
KW - DNA-surfactant complexes
KW - light-induced DNA de-compaction
KW - phase diagram
KW - DNA volume and persistent length
Y1 - 2015
U6 - https://doi.org/10.1002/bip.22575
SN - 0006-3525
SN - 1097-0282
VL - 103
IS - 2
SP - 109
EP - 122
PB - Wiley-Blackwell
CY - Hoboken
ER -
TY - JOUR
A1 - Kulesza, Alexander Jan
A1 - Titov, Evgenii
A1 - Daly, Steven
A1 - Wlodarczyk, Radoslaw
A1 - Megow, Jörg
A1 - Saalfrank, Peter
A1 - Choi, Chang Min
A1 - MacAleese, Luke
A1 - Antoine, Rodolphe
A1 - Dugourd, Philippe
T1 - Excited States of Xanthene Analogues: Photofragmentation and Calculations by CC2 and Time-Dependent Density Functional Theory
JF - ChemPhysChem : a European journal of chemical physics and physical chemistry
N2 - Action spectroscopy has emerged as an analytical tool to probe excited states in the gas phase. Although comparison of gas-phase absorption properties with quantum-chemical calculations is, in principle, straightforward, popular methods often fail to describe many molecules of interest-such as xanthene analogues. We, therefore, face their nano-and picosecond laser-induced photofragmentation with excited-state computations by using the CC2 method and time-dependent density functional theory (TDDFT). Whereas the extracted absorption maxima agree with CC2 predictions, the TDDFT excitation energies are blueshifted. Lowering the amount of Hartree-Fock exchange in the DFT functional can reduce this shift but at the cost of changing the nature of the excited state. Additional bandwidth observed in the photofragmentation spectra is rationalized in terms of multiphoton processes. Observed fragmentation from higher-lying excited states conforms to intense excited-to-excited state transitions calculated with CC2. The CC2 method is thus suitable for the comparison with photofragmentation in xanthene analogues.
KW - density functional calculations
KW - CC2 calculations
KW - multiphoton processes
KW - photofragmentation
KW - xanthenes
Y1 - 2016
U6 - https://doi.org/10.1002/cphc.201600650
SN - 1439-4235
SN - 1439-7641
VL - 17
SP - 3129
EP - 3138
PB - Wiley-VCH
CY - Weinheim
ER -
TY - JOUR
A1 - Kuntze, Kim
A1 - Viljakka, Jani
A1 - Titov, Evgenii
A1 - Ahmed, Zafar
A1 - Kalenius, Elina
A1 - Saalfrank, Peter
A1 - Priimagi, Arri
T1 - Towards low-energy-light-driven bistable photoswitches
BT - ortho-fluoroaminoazobenzenes
JF - Photochemical & photobiological sciences / European Society for Photobiology
N2 - Thermally stable photoswitches that are driven with low-energy light are rare, yet crucial for extending the applicability of photoresponsive molecules and materials towards, e.g., living systems. Combined ortho-fluorination and -amination couples high visible light absorptivity of o-aminoazobenzenes with the extraordinary bistability of o-fluoroazobenzenes. Herein, we report a library of easily accessible o-aminofluoroazobenzenes and establish structure-property relationships regarding spectral qualities, visible light isomerization efficiency and thermal stability of the cis-isomer with respect to the degree of o-substitution and choice of amino substituent. We rationalize the experimental results with quantum chemical calculations, revealing the nature of low-lying excited states and providing insight into thermal isomerization. The synthesized azobenzenes absorb at up to 600 nm and their thermal cis-lifetimes range from milliseconds to months. The most unique example can be driven from trans to cis with any wavelength from UV up to 595 nm, while still exhibiting a thermal cis-lifetime of 81 days.
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Y1 - 2022
U6 - https://doi.org/10.1007/s43630-021-00145-4
SN - 1474-905X
SN - 1474-9092
VL - 21
IS - 2
SP - 159
EP - 173
PB - Springer
CY - Heidelberg
ER -
TY - JOUR
A1 - Malyar, Ivan V.
A1 - Titov, Evgenii
A1 - Lomadze, Nino
A1 - Saalfrank, Peter
A1 - Santer, Svetlana
T1 - Photoswitching of azobenzene-containing self-assembled monolayers as a tool for control over silicon surface electronic properties
JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2 - We report on photoinduced remote control of work function and surface potential of a silicon surface modified with a photosensitive self-assembled monolayer consisting of chemisorbed azobenzene molecules (4-nitroazobenzene). Itwas found that the attachment of the organic monolayer increases the work function by hundreds of meV due to the increase in the electron affinity of silicon substrates. The change in the work function on UV light illumination is more pronounced for the azobenzene jacketed silicon substrate (ca. 250 meV) in comparison to 50 meV for the unmodified surface. Moreover, the photoisomerization of azobenzene results in complex kinetics of thework function change: immediate decrease due to light-driven processes in the silicon surface followed by slower recovery to the initial state due to azobenzene isomerization. This behavior could be of interest for electronic devices where the reaction on irradiation should be more pronounced at small time scales but the overall surface potential should stay constant over time independent of the irradiation conditions. Published by AIP Publishing.
Y1 - 2017
U6 - https://doi.org/10.1063/1.4978225
SN - 0021-9606
SN - 1089-7690
VL - 146
PB - American Institute of Physics
CY - Melville
ER -
TY - JOUR
A1 - Reifarth, Martin
A1 - Bekir, Marek
A1 - Bapolisi, Alain M.
A1 - Titov, Evgenii
A1 - Nusshardt, Fabian
A1 - Nowaczyk, Julius
A1 - Grigoriev, Dmitry
A1 - Sharma, Anjali
A1 - Saalfrank, Peter
A1 - Santer, Svetlana
A1 - Hartlieb, Matthias
A1 - Böker, Alexander
T1 - A dual pH- and light-responsive spiropyrane-based surfactant
BT - investigations on Its switching behavior and remote control over emulsion stability
JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition
N2 - A cationic surfactant containing a spiropyrane unit is prepared exhibiting a dual-responsive adjustability of its surface-active characteristics. The switching mechanism of the system relies on the reversible conversion of the non-ionic spiropyrane (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH-dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli-responsive behavior enables remote-control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH-dependent manipulation of oil-in-water emulsions.
KW - Dual-Responsiveness
KW - Manipulation of Emulsion Stability
KW - Spiropyrane
KW - Surfactant
KW - Switchable Surfactants
KW - pH-Dependent Photoresponsivity
Y1 - 2022
U6 - https://doi.org/10.1002/anie.202114687
SN - 1433-7851
SN - 1521-3773
VL - 61
IS - 21
PB - Wiley-VCH
CY - Weinheim
ER -
TY - JOUR
A1 - Rietze, Clemens
A1 - Titov, Evgenii
A1 - Granucci, Giovanni
A1 - Saalfrank, Peter
T1 - Surface hopping dynamics for azobenzene photoisomerization
BT - effects of packing density on surfaces, fluorination, and excitation wavelength
JF - The journal of physical chemistry : C, Nanomaterials and interfaces
N2 - Azobenzenes easily photoswitch in solution, while their photoisomerization at surfaces is often hindered. In recent work, it was demonstrated by nonadiabatic molecular dynamics with trajectory surface hopping [Titov et al., J. Phys. Chem. Lett. 2016, 7, 3591-3596] that the experimentally observed suppression of trans -> cis isomerization yields in azobenzenes in a densely packed SAM (self-assembled monolayer) [Gahl et al., J. Am. Chem. Soc. 2010, 132, 1831-1838] is dominated by steric hindrance. In the present work, we systematically study by ground-state Langevin and nonadiabatic surface hopping dynamics, the effects of decreasing packing density on (i) UV/vis absorption spectra, (ii) trans -> cis isomerization yields, and (iii) excited-state lifetimes of photoexcited azobenzene. Within the quantum mechanics/ molecular mechanics models adopted here, we find that above a packing density of similar to 3 molecules/nm(2), switching yields are strongly reduced, while at smaller packing densities, the "monomer limit" is quickly approached. The UV/vis absorption spectra, on the other hand, depend on packing density over a larger range (down to at least similar to 1 molecule/nm(2)). Trends for excited-state lifetimes are less obvious, but it is found that lifetimes of pi pi* excited states decay monotonically with decreasing coverage. Effects of fluorination of the switches are also discussed for single, free molecules. Fluorination leads to comparatively large trans -> cis yields, in combination with long pi pi* lifetimes. Furthermore, for selected systems, also the effects of n pi* excitation at longer excitation wavelengths have been studied, which is found to enhance trans -> cis yields for free molecules but can lead to an opposite behavior in densely packed SAMs.
KW - Computational chemistry
KW - Energy
KW - Molecules
KW - Monomers
KW - Oligomers
Y1 - 2020
U6 - https://doi.org/10.1021/acs.jpcc.0c08052
SN - 1932-7447
SN - 1932-7455
VL - 124
IS - 48
SP - 26287
EP - 26295
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Rietze, Clemens
A1 - Titov, Evgenii
A1 - Lindner, Steven
A1 - Saalfrank, Peter
T1 - Thermal isomerization of azobenzenes: on the performance of Eyring transition state theory
JF - Journal of physics : Condensed matter
N2 - The thermal Z -> E (back-) isomerization of azobenzenes is a prototypical reaction occurring in molecular switches. It has been studied for decades, yet its kinetics is not fully understood. In this paper, quantum chemical calculations are performed to model the kinetics of an experimental benchmark system, where a modified azobenzene (AzoBiPyB) is embedded in a metal-organic framework (MOF). The molecule can be switched thermally from cis to trans, under solvent-free conditions. We critically test the validity of Eyring transition state theory for this reaction. As previously found for other azobenzenes (albeit in solution), good agreement between theory and experiment emerges for activation energies and activation free energies, already at a comparatively simple level of theory, B3LYP/6-31G* including dispersion corrections. However, theoretical Arrhenius prefactors and activation entropies are in qualitiative disagreement with experiment. Several factors are discussed that may have an influence on activation entropies, among them dynamical and geometric constraints (imposed by the MOF). For a simpler model-Z -> E isomerization in azobenzene-a systematic test of quantum chemical methods from both density functional theory and wavefunction theory is carried out in the context of Eyring theory. Also, the effect of anharmonicities on activation entropies is discussed for this model system. Our work highlights capabilities and shortcomings of Eyring transition state theory and quantum chemical methods, when applied for the Z -> E (back-) isomerization of azobenzenes under solvent-free conditions.
KW - thermal isomerization
Y1 - 2017
U6 - https://doi.org/10.1088/1361-648X/aa75bd
SN - 0953-8984
SN - 1361-648X
VL - 29
PB - IOP Publ. Ltd.
CY - Bristol
ER -
TY - JOUR
A1 - Schürmann, Robin
A1 - Titov, Evgenii
A1 - Ebel, Kenny
A1 - Kogikoski Junior, Sergio
A1 - Mostafa, Amr
A1 - Saalfrank, Peter
A1 - Milosavljević, Aleksandar R.
A1 - Bald, Ilko
T1 - The electronic structure of the metal-organic interface of isolated ligand coated gold nanoparticles
JF - Nanoscale Advances
N2 - Light induced electron transfer reactions of molecules on the surface of noble metal nanoparticles (NPs) depend significantly on the electronic properties of the metal-organic interface. Hybridized metal-molecule states and dipoles at the interface alter the work function and facilitate or hinder electron transfer between the NPs and ligand. X-ray photoelectron spectroscopy (XPS) measurements of isolated AuNPs coated with thiolated ligands in a vacuum have been performed as a function of photon energy, and the depth dependent information of the metal-organic interface has been obtained. The role of surface dipoles in the XPS measurements of isolated ligand coated NPs is discussed and the binding energy of the Au 4f states is shifted by around 0.8 eV in the outer atomic layers of 4-nitrothiophenol coated AuNPs, facilitating electron transport towards the molecules. Moreover, the influence of the interface dipole depends significantly on the adsorbed ligand molecules. The present study paves the way towards the engineering of the electronic properties of the nanoparticle surface, which is of utmost importance for the application of plasmonic nanoparticles in the fields of heterogeneous catalysis and solar energy conversion.
Y1 - 2022
U6 - https://doi.org/10.1039/d1na00737h
SN - 2516-0230
VL - 4
IS - 6
SP - 1599
EP - 1607
PB - Royal Society of Chemistry
CY - Cambridge
ER -