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DatensammlungAccess status: Open Access ,
Raw data for "Triplet-sensitized switching of high-energy-density norbornadienes for molecular solar thermal energy storage with visible Light"
(2024)
Zähringer, Till J. B.
;
Perez Lopez, Nico
;
Schulte, Robin
;
Schmitz, Matthias
;
Ihmels, Heiko
Norbornadiene-based photoswitches have emerged as promising candidates for harnessing and storing solar energy, holding great promise as a viable solution to meet the growing energy demands. Despite their potential, the effectiveness of their direct photochemical conversion into the resulting quadricyclanes has room for improvement owing to (i) moderate quantum yields, (ii) poor overlap with the solar spectrum and (iii) photochemical back reactions. Herein, we present an approach to enhance the performance of such molecular solar thermal energy storage (MOST) systems through the triplet-sensitized conversion of aryl-substituted norbornadienes. Our study combines deep spectroscopic analyses, irradiation experiments, and quantum mechanical calculations to elucidate the energy transfer mechanism and inherent advantages of the resulting MOST systems. We demonstrate remarkable quantum yields using readily available sensitizers under both LED and solar light irradiation, significantly surpassing those achieved through direct excitation with photons of higher energy. In contrast to the conventional approach, light-induced back reactions of the high-energy products do not play any role, allowing quantitative switching within minutes. These results not only underscore the potential of triplet-sensitized MOST systems to leverage the high energy storage capabilities of multistate photoswitches but they might also stimulate the broader usage of sensitization strategies in photochemical energy conversion.
DatensammlungAccess status: Open Access ,
Raw data for "Efficient energy and electron transfer photocatalysis with a Coulombic dyad"
(2024)
Schmitz, Matthias
;
Bertrams, Maria-Sophie
;
Sell, Arne C.
;
Glaser, Felix
;
Kerzig, Christoph
Photocatalysis holds great promise for changing the way value-added molecules are currently prepared. However, many photocatalytic reactions suffer from quantum yields well below 10 %, hampering the transition from lab-scale reactions to large-scale or even industrial applications. Molecular dyads can be designed such that the beneficial properties of inorganic and organic chromophores are combined, resulting in milder reaction conditions and improved quantum yields of photocatalytic reactions. We have developed a novel approach for obtaining the advantages of molecular dyads without the time- and resource-consuming synthesis of these tailored photocatalysts. Simply by mixing a cationic ruthenium complex with an anionic pyrene derivative in water a salt bichromophore is produced owing to electrostatic interactions. The long-lived organic triplet state is obtained by static and quantitative energy transfer from the preorganized ruthenium complex. We exploited this so-called Coulombic dyad for energy transfer catalysis with similar reactivity and even higher photostability compared to a molecular dyad and reference photosensitizers in several photooxygenations. In addition, it was shown that this system can also be used to maximize the quantum yield of photoredox reactions. This is due to an intrinsically higher cage escape quantum yield after photoinduced electron transfer for purely organic compounds compared to heavy atom-containing molecules. The combination of laboratory-scale as well as mechanistic irradiation experiments with detailed spectroscopic investigations provided deep mechanistic insights into this easy-to-use photocatalyst class.
DatensammlungAccess status: Open Access ,
Raw data for "Mechanistic investigations of polyaza[7]helicene in photoredox and energy transfer catalysis"
(2024)
Rocker, Johannes
;
Zähringer, Till J. B.
;
Schmitz, Matthias
;
Opatz, Till
;
Kerzig, Christoph
Organic photocatalysts frequently possess dual singlet and triplet photoreactivity and a thorough photochemical characterization is essential for efficient light-driven applications. In this article, the mode of action of a polyazahelicene catalyst (Aza-H) was investigated using laser flash photolysis (LFP). The study revealed that the chromophore can function as a singlet-state photoredox catalyst in the sulfonylation/arylation of styrenes and as a triplet sensitizer in energy transfer catalysis. The singlet lifetime is sufficiently long to exploit the exceptional excited state reduction potential for the activation of 4-cyanopyridine. Photoinduced electron transfer generating the radical cation was directly observed confirming the previously proposed mechanism of a three-component reaction. Several steps of the photoredox cycle were investigated separately, providing deep insights into the complex mechanism. The triplet-excited Aza-H, which was studied with quantitative LFP, is formed with a quantum yield of 0.34. The pronounced triplet formation was exploited for the isomerization reaction of (E)-stilbene to the Z-isomer and the cyclization of cinnamyl chloride. Catalyst degradation mainly occurs through the long-lived Aza-H triplet (28 µs), but the photostability is greatly increased when the triplet efficiently reacts in a catalytic cycle such that turnover numbers exceeding 4400 are achievable with this organocatalyst.