@phdthesis{Savatieiev2023, author = {Savatieiev, Oleksandr}, title = {Carbon nitride semiconductors: properties and application as photocatalysts in organic synthesis}, school = {Universit{\"a}t Potsdam}, pages = {272}, year = {2023}, abstract = {Graphitic carbon nitrides (g-CNs) are represented by melon-type g-CN, poly(heptazine imides) (PHIs), triazine-based g-CN and poly(triazine imide) with intercalated LiCl (PTI/Li+Cl‒). These materials are composed of sp2-hybridized carbon and nitrogen atoms; C:N ratio is close to 3:4; the building unit is 1,3,5-triazine or tri-s-triazine; the building units are interconnected covalently via sp2-hybridized nitrogen atoms or NH-moieties; the layers are assembled into a stack via weak van der Waals forces as in graphite. Due to medium band gap (~2.7 eV) g-CNs, such as melon-type g-CN and PHIs, are excited by photons with wavelength ≤ 460 nm. Since 2009 g-CNs have been actively studied as photocatalysts in evolution of hydrogen and oxygen - two half-reactions of full water splitting, by employing corresponding sacrificial agents. At the same time application of g-CNs as photocatalysts in organic synthesis has been remaining limited to few reactions only. Cumulative Habilitation summarizes research work conducted by the group 'Innovative Heterogeneous Photocatalysis' between 2017-2023 in the field of carbon nitride organic photocatalysis, which is led by Dr. Oleksandr Savatieiev. g-CN photocatalysts activate molecules, i.e. generate their more reactive open-shell intermediates, via three modes: i) Photoinduced electron transfer (PET); ii) Excited state proton-coupled electron transfer (ES-PCET) or direct hydrogen atom transfer (dHAT); iii) Energy transfer (EnT). The scope of reactions that proceed via oxidative PET, i.e. one-electron oxidation of a substrate to the corresponding radical cation, are represented by synthesis of sulfonylchlorides from S-acetylthiophenols. The scope of reactions that proceed via reductive PET, i.e. one-electron reduction of a substrate to the corresponding radical anion, are represented by synthesis of γ,γ-dichloroketones from the enones and chloroform. Due to abundance of sp2-hybridized nitrogen atoms in the structure of g-CN materials, they are able to cleave X-H bonds in organic molecules and store temporary hydrogen atom. ES-PCET or dHAT mode of organic molecules activation to the corresponding radicals is implemented for substrates featuring relatively acidic X-H bonds and those that are characterized by low bond dissociation energy, such as C-H bond next to the heteroelements. On the other hand, reductively quenched g-CN carrying hydrogen atom reduces a carbonyl compound to the ketyl radical via PCET that is thermodynamically more favorable pathway compared to the electron transfer. The scope of these reactions is represented by cyclodimerization of α,β-unsaturated ketones to cyclopentanoles. g-CN excited state demonstrates complex dynamics with the initial formation of singlet excited state, which upon intersystem crossing produces triplet excited state that is characterized by the lifetime > 2 μs. Due to long lifetime, g-CN activate organic molecules via EnT. For example, g-CN sensitizes singlet oxygen, which is the key intermediate in the dehydrogenation of aldoximes to nitrileoxides. The transient nitrileoxide undergoes [3+2]-cycloaddition to nitriles and gives oxadiazoles-1,2,4. PET, ES-PCET and EnT are fundamental phenomena that are applied beyond organic photocatalysis. Hybrid composite is formed by combining conductive polymers, such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) with potassium poly(heptazine imide) (K-PHI). Upon PET, K-PHI modulated population of polarons and therefore conductivity of PEDOT:PSS. The initial state of PEDOT:PSS is recovered upon material exposure to O2. K-PHI:PEDOT:PSS may be applied in O2 sensing. In the presence of electron donors, such as tertiary amines and alcohols, and irradiation with light, K-PHI undergoes photocharging - the g-CN material accumulates electrons and charge-compensating cations. Such photocharged state is stable under anaerobic conditions for weeks, but at the same time it is a strong reductant. This feature allows decoupling in time light harvesting and energy storage in the form of electron-proton couples from utilization in organic synthesis. The photocharged state of K-PHI reduces nitrobenzene to aniline, and enables dimerization of α,β-unsaturated ketones to hexadienones in dark.}, language = {en} } @article{FudickarBauchIhmelsetal.2021, author = {Fudickar, Werner and Bauch, Marcel and Ihmels, Heiko and Linker, Torsten}, title = {DNA-triggered enhancement of singlet oxygen production by pyridinium alkynylanthracenes}, series = {Chemistry - a European journal}, volume = {27}, journal = {Chemistry - a European journal}, number = {54}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1521-3765}, doi = {10.1002/chem.202101918}, pages = {13591 -- 13604}, year = {2021}, abstract = {There is an ongoing interest in O-1(2) sensitizers, whose activity is selectively controlled by their interaction with DNA. To this end, we synthesized three isomeric pyridinium alkynylanthracenes 2 o-p and a water-soluble trapping reagent for O-1(2). In water and in the absence of DNA, these dyes show a poor efficiency to sensitize the photooxygenation of the trapping reagent as they decompose due to electron transfer processes. In contrast, in the presence of DNA O-1(2) is generated from the excited DNA-bound ligand. The interactions of 2 o-p with DNA were investigated by thermal DNA melting studies, UV/vis and fluorescence spectroscopy, and linear and circular dichroism spectroscopy. Our studies revealed an intercalative binding with an orientation of the long pyridyl-alkynyl axis parallel to the main axis of the DNA base pairs. In the presence of poly(dA : dT), all three isomers show an enhanced formation of singlet oxygen, as indicated by the reaction of the latter with the trapping reagent. With green light irradiation of isomer 2 o in poly(dA : dT), the conversion rate of the trapping reagent is enhanced by a factor >10. The formation of O-1(2) was confirmed by control experiments under anaerobic conditions, in deuterated solvents, or by addition of O-1(2) quenchers. When bound to poly(dG : dC), the opposite effect was observed only for isomers 2 o and 2 m, namely the trapping reagent reacted significantly slower. Overall, we showed that pyridinium alkynylanthracenes are very useful intercalators, that exhibit an enhanced photochemical O-1(2) generation in the DNA-bound state.}, language = {en} } @article{PruefertUrbanFischeretal.2020, author = {Pr{\"u}fert, Chris and Urban, Raphael David and Fischer, Tillmann Georg and Villatoro, Jos{\´e} Andr{\´e}s and Riebe, Daniel and Beitz, Toralf and Belder, Detlev and Zeitler, Kirsten and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {In situ monitoring of photocatalyzed isomerization reactions on a microchip flow reactor by IR-MALDI ion mobility spectrometry}, series = {Analytical and bioanalytical chemistry : a merger of Fresenius' journal of analytical chemistry, Analusis and Quimica analitica}, volume = {412}, journal = {Analytical and bioanalytical chemistry : a merger of Fresenius' journal of analytical chemistry, Analusis and Quimica analitica}, number = {28}, publisher = {Springer}, address = {Heidelberg}, issn = {1618-2642}, doi = {10.1007/s00216-020-02923-y}, pages = {7899 -- 7911}, year = {2020}, abstract = {The visible-light photocatalyticE/Zisomerization of olefins can be mediated by a wide spectrum of triplet sensitizers (photocatalysts). However, the search for the most efficient photocatalysts through screenings in photo batch reactors is material and time consuming. Capillary and microchip flow reactors can accelerate this screening process. Combined with a fast analytical technique for isomer differentiation, these reactors can enable high-throughput analyses. Ion mobility (IM) spectrometry is a cost-effective technique that allows simple isomer separation and detection on the millisecond timescale. This work introduces a hyphenation method consisting of a microchip reactor and an infrared matrix-assisted laser desorption ionization (IR-MALDI) ion mobility spectrometer that has the potential for high-throughput analysis. The photocatalyzedE/Zisomerization of ethyl-3-(pyridine-3-yl)but-2-enoate (E-1) as a model substrate was chosen to demonstrate the capability of this device. Classic organic triplet sensitizers as well as Ru-, Ir-, and Cu-based complexes were tested as catalysts. The ionization efficiency of theZ-isomer is much higher at atmospheric pressure which is due to a higher proton affinity. In order to suppress proton transfer reactions by limiting the number of collisions, an IM spectrometer working at reduced pressure (max. 100 mbar) was employed. This design reduced charge transfer reactions and allowed the quantitative determination of the reaction yield in real time. Among 14 catalysts tested, four catalysts could be determined as efficient sensitizers for theE/Zisomerization of ethyl cinnamate derivativeE-1. Conversion rates of up to 80\% were achieved in irradiation time sequences of 10 up to 180 s. With respect to current studies found in the literature, this reduces the acquisition times from several hours to only a few minutes per scan.}, language = {en} } @article{WolfHolzmeierWagneretal.2017, author = {Wolf, Thomas J. A. and Holzmeier, Fabian and Wagner, Isabella and Berrah, Nora and Bostedt, Christoph and Bozek, John and Bucksbaum, Phil and Coffee, Ryan and Cryan, James and Farrell, Joe and Feifel, Raimund and Martinez, Todd J. and McFarland, Brian and Mucke, Melanie and Nandi, Saikat and Tarantelli, Francesco and Fischer, Ingo and G{\"u}hr, Markus}, title = {Observing Femtosecond Fragmentation Using Ultrafast X-ray-Induced Auger Spectra}, series = {Applied sciences}, volume = {7}, journal = {Applied sciences}, number = {7}, publisher = {MDPI}, address = {Basel}, issn = {2076-3417}, doi = {10.3390/app7070681}, pages = {11}, year = {2017}, abstract = {Molecules often fragment after photoionization in the gas phase. Usually, this process can only be investigated spectroscopically as long as there exists electron correlation between the photofragments. Important parameters, like their kinetic energy after separation, cannot be investigated. We are reporting on a femtosecond time-resolved Auger electron spectroscopy study concerning the photofragmentation dynamics of thymine. We observe the appearance of clearly distinguishable signatures from thymines neutral photofragment isocyanic acid. Furthermore, we observe a time-dependent shift of its spectrum, which we can attribute to the influence of the charged fragment on the Auger electron. This allows us to map our time-dependent dataset onto the fragmentation coordinate. The time dependence of the shift supports efficient transformation of the excess energy gained from photoionization into kinetic energy of the fragments. Our method is broadly applicable to the investigation of photofragmentation processes.}, language = {en} } @article{MaticSchlaad2018, author = {Matic, Aleksandar and Schlaad, Helmut}, title = {Thiol-ene photofunctionalization of 1,4-polymyrcene}, series = {Polymer international}, volume = {67}, journal = {Polymer international}, number = {5}, publisher = {Wiley}, address = {Hoboken}, issn = {0959-8103}, doi = {10.1002/pi.5534}, pages = {500 -- 505}, year = {2018}, abstract = {1,4-Polymyrcene was synthesized by anionic polymerization of -myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, ethyl 2-mercaptopropionate and 2-methyl-2-propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4-polymyrcene decreased in the order 1 degrees thiol (ca 95\%) > 2 degrees thiol (ca 80\%) > 3 degrees thiol (<5\%), due to the reversibility of the thiol-ene reaction. Remarkably, thiol addition to the side-chain double bonds was 8 - 10 times (1 degrees thiol) or 24 times (2 degrees thiol) faster than to the main-chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10-fold excess of thiol with respect to myrcene units, the thiol-ene addition was accompanied by chain coupling reactions, which in the extreme case of 3 degrees thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl-thioglycolate-functionalized 1,4-polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. (c) 2018 Society of Chemical Industry}, language = {en} } @article{HardyBertinTorresRendonetal.2018, author = {Hardy, John G. and Bertin, Annabelle and Torres-Rendon, Jose Guillermo and Leal-Egana, Aldo and Humenik, Martin and Bauer, Felix and Walther, Andreas and C{\"o}lfen, Helmut and Schlaad, Helmut and Scheibel, Thomas R.}, title = {Facile photochemical modification of silk protein-based biomaterials}, series = {Macromolecular bioscience}, volume = {18}, journal = {Macromolecular bioscience}, number = {11}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-5187}, doi = {10.1002/mabi.201800216}, pages = {6}, year = {2018}, abstract = {Silk protein-based materials show promise for application as biomaterials for tissue engineering. The simple and rapid photochemical modification of silk protein-based materials composed of either Bombyx mori silkworm silk or engineered spider silk proteins (eADF4(C16)) is reported. Radicals formed on the silk-based materials initiate the polymerization of monomers (acrylic acid, methacrylic acid, or allylamine) which functionalize the surface of the silk materials with poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), or poly(allylamine) (PAAm). To demonstrate potential applications of this type of modification, the polymer-modified silks are mineralized. The PAA- and PMAA-functionalized silks are mineralized with calcium carbonate, whereas the PAAm-functionalized silks are mineralized with silica, both of which provide a coating on the materials that may be useful for bone tissue engineering, which will be the subject of future investigations.}, language = {en} } @article{WeisHessKircheretal.2019, author = {Weis, Philipp and Hess, Andreas and Kircher, Gunnar and Huang, Shilin and Auernhammer, G{\"u}nter K. and Koynov, Kaloian and Butt, Hans-J{\"u}rgen and Wu, Si}, title = {Effects of Spacers on Photoinduced Reversible Solid-to-Liquid Transitions of Azobenzene-Containing Polymers}, series = {Chemistry - a European journal}, volume = {25}, journal = {Chemistry - a European journal}, number = {46}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201902273}, pages = {10946 -- 10953}, year = {2019}, abstract = {Photoisomerization in some azobenzene-containing polymers (azopolymers) results in reversible solid-to-liquid transitions because trans- and cis-azopolymers have different glass transition temperatures. This property enables photoinduced healing and processing of azopolymers with high spatiotemporal resolution. However, a general lack of knowledge about the influence of the polymer structure on photoinduced reversible solid-to-liquid transitions hinders the design of such novel polymers. Herein, the synthesis and photoresponsive behavior of new azopolymers with different lengths of spacers between the polymer backbone and the azobenzene group on the side chain are reported. Azopolymers with no and 20 methylene spacers did not show photoinduced solid-to-liquid transitions. Azopolymers with 6 or 12 methylene spacers showed photoinduced solid-to-liquid transitions. This study demonstrates that spacers are essential for azopolymers with photoinduced reversible solid-to-liquid transitions, and thus, gives an insight into how to design azopolymers for photoinduced healing and processing.}, language = {en} } @article{GoebelHesemannFriedrichetal.2014, author = {Goebel, Ronald and Hesemann, Peter and Friedrich, Alwin and Rothe, Regina and Schlaad, Helmut and Taubert, Andreas}, title = {Modular thiol-ene chemistry approach towards mesoporous silica monoliths with organically modified pore walls}, series = {Chemistry - a European journal}, volume = {20}, journal = {Chemistry - a European journal}, number = {52}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201403982}, pages = {17579 -- 17589}, year = {2014}, abstract = {The surface modification of mesoporous silica monoliths through thiol-ene chemistry is reported. First, mesoporous silica monoliths with vinyl, allyl, and thiol groups were synthesized through a sol-gel hydrolysis-poly-condensation reaction from tetramethyl orthosilicate (TMOS) and vinyltriethoxysilane, allyltriethoxysilane, and (3-mercaptopropyl) trimethoxysilane, respectively. By variation of the molar ratio of the comonomers TMOS and functional silane, mesoporous silica objects containing different amounts of vinyl, allyl, and thiol groups were obtained. These intermediates can subsequently be derivatized through radical photoaddition reactions either with a thiol or an olefin, depending on the initial pore wall functionality, to yield silica monoliths with different pore-wall chemistries. Nitrogen sorption, small-angle X-ray scattering, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis, and redox titration demonstrate that the synthetic pathway influences the morphology and pore characteristics of the resulting monoliths and also plays a significant role in the efficiency of functionalization. Moreover, the different reactivity of the vinyl and allyl groups on the pore wall affects the addition reaction, and hence, the degree of the pore-wall functionalization. This report demonstrates that thiol-ene photoaddition reactions are a versatile platform for the generation of a large variety of organically modified silica monoliths with different pore surfaces.}, language = {en} } @article{LuoUtechtDokicetal.2011, author = {Luo, Ying and Utecht, Manuel Martin and Dokic, Jadranka and Korchak, Sergey and Vieth, Hans-Martin and Haag, Rainer and Saalfrank, Peter}, title = {Cis-trans isomerisation of substituted aromatic imines a comparative experimental and theoretical study}, series = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, volume = {12}, journal = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, number = {12}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1439-4235}, doi = {10.1002/cphc.201100179}, pages = {2311 -- 2321}, year = {2011}, abstract = {The cis-trans isomerisation of N-benzylideneaniline (NBA) and derivatives containing a central C=N bond has been investigated experimentally and theoretically. Eight different NBA molecules in three different solvents were irradiated to enforce a photochemical trans (hv) -> cis isomerisation and the kinetics of the thermal backreaction cis (Delta)-> trans were determined by NMR spectroscopy measurements in the temperature range between 193 and 288 K. Theoretical calculations using density functional theory and Eyring transition-state theory were carried out for 12 different NBA species in the gas phase and three different solvents to compute thermal isomerisation rates of the thermal back reaction. While the computed absolute rates are too large, they reveal and explain experimental trends. Time-dependent density functional theory provides optical spectra for vertical transitions and excitation energy differences between trans and cis forms. Together with isomerisation rates, the latter can be used to identify "optimal switches" with good photochromicity and reasonable thermal stability.}, language = {en} } @article{FuechselTremblayKlamrothetal.2012, author = {F{\"u}chsel, Gernot and Tremblay, Jean Christophe and Klamroth, Tillmann and Saalfrank, Peter}, title = {Selective excitation of molecule-surface vibrations in H2 and D2 dissociatively adsorbed on Ru(0001)}, series = {Israel journal of chemistry}, volume = {52}, journal = {Israel journal of chemistry}, number = {5}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0021-2148}, doi = {10.1002/ijch.201100097}, pages = {438 -- 451}, year = {2012}, abstract = {In this contribution we report about the selective vibrational excitation of H2 and D2 on Ru(0001) as an example for nonadiabatic coupling of an open quantum system to a dissipative environment. We investigate the possibility of achieving state-selective vibrational excitations of H2 and D2 adsorbed on a Ru(0001) surface using picosecond infrared laser pulses. The systems behavior is explored using pulses that are rationally designed and others that are optimized using a time-local variant of Optimal Control Theory. The effects of dissipation on the laser-driven dynamics are studied using the reduced-density matrix formalism. The non-adiabatic couplings between adsorbate and surface are computed perturbatively, for which our recently introduced state-resolved anharmonic rate model is used. It is shown that mode- and state-selective excitation can be achieved in the absence of dissipation when using optimized laser pulses. The inclusion of dissipation in the model reduces the state selectivity and the population transfer yield to highly excited states. In this case, mode activation is most effectively realized by a rational pulse of carefully chosen duration rather than by a locally optimized pulse.}, language = {en} }