@article{GaebertRosenstinglLinsleretal.2020, author = {G{\"a}bert, Chris and Rosenstingl, Tobias and Linsler, Dominic and Dienwiebel, Martin and Reinicke, Stefan}, title = {Programming viscosity in silicone oils}, series = {ACS applied polymer materials}, volume = {2}, journal = {ACS applied polymer materials}, number = {12}, publisher = {ACS Publications}, address = {Washington, DC}, issn = {2637-6105}, doi = {10.1021/acsapm.0c00794}, pages = {5460 -- 5468}, year = {2020}, abstract = {Programmable oils feature tunable viscosity and therefore possess potential for technical improvements and innovative solutions in many lubricated applications. Herein, we describe the first assessment of the variability of rheological properties of light-programmable 9-anthracene ester-terminated polydimethylsiloxanes (PDMS-As), including implications that arise with UV-light as an external trigger. We applied a modified rheometer setup that enables the monitoring of dynamic moduli during exposure to UV-light. The reversible dimerization of anthracene esters is used to either link PDMS chains by UV-A radiation (365 nm) or cleave chains by UV-C radiation (254 nm) or at elevated temperatures (>130 degrees C). Thermal cleavage fully restores the initial material properties, while the photochemical cleavage of dimers occurs only to a limited extent. Prolonged UV radiation causes material damage and in turn reduces the range of programmable rheological properties. The incomplete cleavage contributes to a gradual buildup of viscosity over a course of several switching cycles, which we suggest to result from chain length-dependent reaction kinetics. Material property gradients induced during radiation due to attenuation of the light beam upon its passing through the oil layer have to be considered, emphasizing the need for proper mixing protocols during the programming step. The material in focus shows integrated photorheology and is suggested to improve the performance of silicone oils in friction systems.}, language = {en} } @article{SchwarzeKellingSperlichetal.2021, author = {Schwarze, Thomas and Kelling, Alexandra and Sperlich, Eric and Holdt, Hans-J{\"u}rgen}, title = {Influence of regioisomerism in 9-anthracenyl-substituted dithiodicyanoethene derivatives on photoinduced electron transfer controlled by intramolecular charge transfer}, series = {ChemPhotoChem}, volume = {5}, journal = {ChemPhotoChem}, number = {10}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2367-0932}, doi = {10.1002/cptc.202100070}, pages = {911 -- 914}, year = {2021}, abstract = {In this paper, we report on the fluorescence behaviour of three regioisomers which consist of two 9-anthracenyl fluorophores and of differently substituted dithiodicyanoethene moieties. These isomeric fluorescent probes show different quantum yields (phi(f)). In these probes, an oxidative photoinduced electron transfer (PET) from the excited 9-anthracenyl fluorophore to the dithiodicyanoethene unit quenches the fluorescence. This quenching process is accelerated by an intramolecular charge transfer (ICT) of the push-pull pi-electron system of the dithiodicyanoethene group. The acceleration of the PET depends on the strength of the ICT unit. The higher the dipole moment of the ICT unit, the stronger the observed fluorescence quenching. To the best of our knowledge, this is the first report of a regioisomeric influence on an oxidative PET by an ICT.}, language = {en} }