@article{WolfSanchezYangetal.2019, author = {Wolf, Thomas J. A. and Sanchez, David M. and Yang, J. and Parrish, R. M. and Nunes, J. P. F. and Centurion, M. and Coffee, R. and Cryan, J. P. and G{\"u}hr, Markus and Hegazy, Kareem and Kirrander, Adam and Li, R. K. and Ruddock, J. and Shen, Xiaozhe and Vecchione, T. and Weathersby, S. P. and Weber, Peter M. and Wilkin, K. and Yong, Haiwang and Zheng, Q. and Wang, X. J. and Minitti, Michael P. and Martinez, Todd J.}, title = {The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction}, series = {Nature chemistry}, volume = {11}, journal = {Nature chemistry}, number = {6}, publisher = {Nature Publ. Group}, address = {London}, issn = {1755-4330}, doi = {10.1038/s41557-019-0252-7}, pages = {504 -- 509}, year = {2019}, abstract = {The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subangstrom length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.}, language = {en} } @article{WessigPick2011, author = {Wessig, Pablo and Pick, Charlotte}, title = {Photochemical synthesis and properties of axially chiral naphthylpyridines}, series = {Journal of photochemistry and photobiology : A, Chemistry}, volume = {222}, journal = {Journal of photochemistry and photobiology : A, Chemistry}, number = {1}, publisher = {Elsevier}, address = {Lausanne}, issn = {1010-6030}, doi = {10.1016/j.jphotochem.2011.06.006}, pages = {263 -- 265}, year = {2011}, abstract = {Five alkynyl pyridines were prepared and cyclized to naphthylpyridines as the main products in the course of a Photo-Dehydro-Diels-Alder reaction. Four of the final products are axially chiral and the determination of the rotational barrier by DFT calculations, dynamic NMR and H PLC experiments is demonstrated. (C) 2011 Elsevier B.V. All rights reserved.}, language = {en} } @article{WessigKrebs2021, author = {Wessig, Pablo and Krebs, Saskia}, title = {N-aroylsulfonamide-photofragmentation (ASAP)}, series = {European journal of organic chemistry}, volume = {2021}, journal = {European journal of organic chemistry}, number = {46}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.202100955}, pages = {6367 -- 6374}, year = {2021}, abstract = {The photochemical fragmentation of N-aroylsulfonamides 9 (ASAP) is a powerful method for the preparation of various biaryls. Compounds 9 are easily accessible in two steps from amines by treatment with arenesulfonyl chlorides and aroyl chlorides. Many of these compounds were prepared for the first time. The irradiation takes place in a previously developed continuous-flow reactor using inexpensive UVB or UVC fluorescent lamps. Isocyanates and sulphur dioxide are formed as the only by-products. The ASAP tolerates a variety of functional groups and is even suited for the preparation of phenylnaphthalenes and terphenyls. The ASAP mechanism was elucidated by interaction of photophysical and quantum chemical (DFT) methods and revealed a spirocyclic biradical as key intermediate.}, language = {en} } @phdthesis{Arya2020, author = {Arya, Pooja}, title = {Light controlled active and passive motion of colloidal particles}, doi = {10.25932/publishup-48388}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-483880}, school = {Universit{\"a}t Potsdam}, pages = {xvii, 183}, year = {2020}, abstract = {In this dissertation we introduce a concept of light driven active and passive manipulation of colloids trapped at solid/liquid interface. The motion is induced due to generation of light driven diffusioosmotic flow (LDDO) upon irradiation with light of appropriate wavelength. The origin of the flow is due to osmotic pressure gradient resulting from a concentration gradient at the solid/liquid interface of the photosensitive surfactant present in colloidal dispersion. The photosensitive surfactant consists of a cationic head group and a hydrophobic tail in which azobenzene group is integrated in. The azobenzene is known to undergo reversible photo-isomerization from a stable trans to a meta stable cis state under irradiation with UV light. Exposure to light of larger wavelength results in back photo-isomerization from cis to trans state. The two isomers have different molecular properties, for instance, trans isomer has a rod like structure and low polarity (0 dipole moment), whereas cis one is bent and has a dipole moment of ~3 Debye. Being integrated in the hydrophobic tail of the surfactant molecule, the azobenzene state determines the hydrophobicity of the whole molecule: in the trans state the surfactant is more hydrophobic than in the cis-state. In this way many properties of the surfactant such as the CMC, solubility and the interaction potential with a solid surface can be altered by light. When the solution containing such a surfactant is irradiated with focused light, a concentration gradient of different isomers is formed near the boundary of the irradiated area near the solid surface resulting in osmotic pressure gradient. The generated diffusioosmotic (DO) flow carries the particles passively along. The local-LDDO flow can be generated around and by each particle when mesoporous silica colloids are dispersed in the surfactant solution. This is because porous particles act as a sink/source which absorbs azobenzene molecule in trans state and expels it when it is in the cis state. The DO flows generated at each particle interact resulting in aggregation or separation depending upon the initial state of surfactant molecules. The kinetic of aggregation and separation can be controlled and manipulated by altering the parameters such as the wavelength and intensity of the applied light, as well as surfactant and particle concentration. Using two wavelengths simultaneously allows for dynamic gathering and separation creating fascinating patterns such as 2D disk of well separated particles or establishing collective complex behaviour of particle ensemble as described in this thesis. The mechanism of l-LDDO is also used to generate self-propelled motion. This is possible when half of the porous particle is covered by metal layer, basically blocking the pores on one side. The LDDO flow generated on uncapped side pushes the particle forward resulting in a super diffusive motion. The system of porous particle and azobenzene containing surfactant molecule can be utilized for various application such as drug delivery, cargo transportation, self-assembling, micro motors/ machines or micro patterning.}, language = {en} } @article{WessigPickSchilde2011, author = {Wessig, Pablo and Pick, Charlotte and Schilde, Uwe}, title = {First example of an atropselective dehydro-Diels-Alder (ADDA) reaction}, series = {Tetrahedron letters}, volume = {52}, journal = {Tetrahedron letters}, number = {32}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2011.06.024}, pages = {4221 -- 4223}, year = {2011}, abstract = {A new concept of a stereoselective synthesis of axially chiral biaryls, formed in the course of the dehydro-Diels-Alder (DDA) reaction, has been disclosed. It is based on asymmetric induction of the newly formed chirality axis by a chirality center, which is present in the two synthesized DDA reactants. Depending on the different length of the linkers joining the alkyne moieties the DDA reaction may be triggered photochemically or thermally, where only the thermal variant was stereoselective.}, language = {en} }