Benjamin Dietzek’s research while affiliated with Friedrich Schiller University Jena and other places

Triplet–triplet annihilation upconversion is a bimolecular process converting low-energy photons into high-energy photons. Here, we report a calcium-sensing system working via triplet–triplet annihilation (TTA) upconverted emission. The probe itself was obtained by covalent conjugation of a blue emitter, perylene, with a calcium-chelating moiety, and it was sensitized by the red-light-absorbing photosensitizer palladium(II) tetraphenyltetrabenzoporphyrin (PdTPTBP). Sensing was selective for Ca²⁺ and occurred in the micromolar domain. In deoxygenated conditions, the TTA upconverted luminescence gradually appeared upon adding an increasing concentration of calcium ions, to reach a maximum upconversion quantum yield of 0.0020.

In the frame of our research aiming to develop efficient triplet-emitting materials, we are exploring the concept of introducing additional heavy atoms into cyclometalated transition metal complexes to enhance intersystem-crossing...

We present a method of enabling photochemical reactions in water by using biomimetic, water-soluble liposomes and a specifically functionalized perylene diimide chromophore. Linking two flexible saturated C4-alkyl chains with terminal positively charged trimethylammonium groups to the rigid perylene diimide core yielded [1]2+ allowing for its co-assembly at the lipid bilayer interface of DOPG liposomes (DOPG = 1,2-dioleoyl-sn-glycero-3-phospho-(1'-rac-glycerol)) with a preferred orientation and in close proximity to the water interface. According to molecular dynamics simulations the chromophore aligns preferably parallel to the membrane surface which is supported by confocal microscopy. Irradiation experiments with visible light and in the presence of a negatively charged, water-soluble oxidant were slower in the DOPG-membrane than under acetonitrile-water reaction conditions. The generated radical species was characterized by EPR spectroscopy in an acetonitrile-water mixture and associated to the DOPG-membrane. Time-resolved emission studies revealed a static quenching process for the initial electron transfer from photoexcited [1]2+ to the water soluble oxidant. The findings presented in this study yield design principles for the functionalization of lipid bilayer membranes which will be relevant for the molecular engineering of artificial cellular organelles and nano-reactors based on biomimetic vesicles and membranes.

Artificial photosynthesis for hydrogen production is an important element in the search for green energy sources. The incorporation of photoactive units into mechanically stable 2D materials paves the way toward the realization of ultrathin membranes as mimics for leaves. Here we present and compare two concepts to introduce a photoactive Ru(II) polypyridine complex into ~1 nm thick carbon nanomembranes (CNMs) generated by low‐energy electron irradiation induced cross‐linking of aromatic self‐assembled monolayers. The photoactive units are either directly incorporated into the CNM scaffold or covalently grafted to its surface. We characterize Ru(II) CNMs using X‐ray photoelectron, surface‐enhanced Raman, photothermal deflection spectroscopy, atomic force, scanning electron microscopy, and study their photoactivity in graphene field‐effect devices. Therewith, we explore the applicability of low‐energy electron irradiation of metal complexes for photosensitizer nanosheet formation.

We report that the homogeneous light-driven hydrogen evolution reaction (HER) can be significantly enhanced by the presence of seemingly innocent ammonium (NH4+) cations. Expermiental studies with different catalysts, photosensitizers and...

The high natural abundance of aluminium makes the respective fluorophores attractive for various optical applications, but photoluminescence quantum yields above 0.7 have yet not been reported for solutions of aluminium complexes. In this contribution, a dinuclear aluminium(III) complex featuring enhanced photoluminescence properties is described. Its facile one‐pot synthesis originates from a readily available precursor and trimethyl aluminium. In solution, the complex exhibits an unprecedented photoluminescence quantum yield near unity (Φabsolute 1.0±0.1) and an excited‐state lifetime of 2.3 ns. In the solid state, J‐aggregation and aggregation‐caused quenching are noted, but still quantum yields of 0.6 are observed. Embedding the complex in electrospun non‐woven fabrics yields a highly fluorescent fleece possessing a quantum yield of 0.9±0.04.

The high natural abundance of aluminium makes the respective fluorophores attractive for various optical applications, but photoluminescence quantum yields above 0.7 have yet not been reported for solutions of aluminium complexes. In this contribution, a dinuclear aluminium(III) complex featuring enhanced photoluminescence properties is described. Its facile one‐pot synthesis originates from a readily available precursor and trimethyl aluminium. In solution, the complex exhibits an unprecedented photoluminescence quantum yield near unity (Φabsolute 1.0 ± 0.1) and an excited‐state lifetime of 2.3 ns. In the solid state, J‐aggregation and aggregation‐caused quenching are noticed, but still quantum yields of 0.6 are observed. Embedding the complex in electrospun non‐woven fabrics yields a highly fluorescent fleece possessing a quantum yield of 0.9 ± 0.04.

In recent years, functional molecular nanosheets have attracted much attention in the fields of sensors and energy storage. Here, we present an approach for the synthesis of photoactive metal-organic nanosheets with ultimate molecular thickness. To this end, we apply low-energy electron irradiation induced cross-linking of 4'-(2,2':6',2''-terpyridine-4'-yl)-1,1'-biphenyl-4-thiol self-assembled monolayers on gold to convert them into functional ∼1 nm thick carbon nanomembranes possessing the ability to reversibly complex lanthanide ions (Ln-CNMs). The obtained Ln-CNMs can be prepared on a large-scale (>10 cm2) and inherit the photoactivity of the pristine terpyridine lanthanide complex (Ln(III)-tpy). Moreover, they possess mechanical stability as free-standing sheets over micrometer sized openings. The presented methodology paves a simple and robust way for the preparation of ultrathin nanosheets with tailored photoactive properties for application in photocatalytic and energy conversion devices.

In situ spectroelectrochemical studies focussing on the Franck-Condon region and sub-ns electron transfer processes in Ru(II)-tpphz-Pt(II) based photocatalysts reveal that single-electron reduction effectively hinders intramolecular electron transfer between the photoexcited...