Inlay

Professor of Chemistry at University of Basel, Switzerland

Macrocyclic Rh(I) complexes stack into tetramers and unlock red absorption and NIR luminescence Alex Bukvic and Mathis Brändlin in @jacs.acspublications.org pubs.acs.org/doi/10.1021/...

Expanding Thermodynamic and Kinetic Frontiers in Molecular Photocatalysis Extreme redox potentials, solvated electrons, upconversion, ultrafast photo-dissociation, slow uphill reactions and beyond @pubs.acs.org pubs.acs.org/doi/10.1021/...

A molecular dyad of an iron complex covalently bound to an annihilator exhibits three photoactive excited states — singlet, doublet, and triplet — enabling homomolecular upconversion Florian Doettinger, Jonathan Sagaya, Giacomo Morselli in @jacs.acspublications.org pubs.acs.org/doi/10.1021/...

Molecular Design Principles for Achieving High-Efficiency Light-Induced Charge Separation at the Nanometer Scale Mathis Brändlin and Felix Himmelreich in jacsau.bsky.social pubs.acs.org/doi/full/10....

Switching Spin‐States: Spin Crossover vs. Coordination‐Induced Spin‐State Switching - Hörner - 2024 - European Journal of Inorganic Chemistry - Wiley Online Library chemistry-europe.onlinelibrary.wiley.com/doi/full/10....

New insights into primary and secondary coordination sphere effects in Rh(I) dimers with NIR emission - published in @angewandtechemie.bsky.social Huge thanks to @wengeroliver.bsky.social for exceptional mentorship and Giacomo Morselli for great collaboration doi.org/10.1002/anie.6066376

The first online symposium organized by the @gdch.de Division of Photochemistry will take place next week (Nov. 5, 2025, 3 pm CET zone). tu-braunschweig.webex.com/tu-braunschw... key: Photo2025 5 talks by talented students (one will be awarded🎉) followed by a plenary lecture. Save the date. ✍️

Exploring metal-centered photoredox reactivity? 🚀Don’t forget to look at the spin-state landscape and the role of reorganisation energy, they can make a difference 😉 Huge thanks to Bekah for leading the experiments and shaping the story🥳 a true collaborative effort!😃 pubs.acs.org/doi/10.1021/...

What happens if you substitute all protons by halogens in a photoactive complex? In our new publication, we show how ligand perhalogenation reshapes redox & photophysical properties in Ni(0) complexes. @wengeroliver.bsky.social in cooperation with Malischeski-group doi.org/10.1021/acs....

Researchers from the SNI network have developed a new sensor system based on platinum #nanostructures that allows the optical differentiation of terpene enantiomers at the molecular level. Published in @angewandtechemie.bsky.social nanoscience.unibas.ch/en/news/deta... @unibas.ch #nanoscience

gerald-hoerner.bsky.social

Swiss Nanoscience Institute, University of Basel

Strategic ligand engineering is essential for the development of new photoactive transition metal complexes. One such application is the control of supramolecular, one-dimensional stacking of square-planar d8-organometallic systems. Here, we report the synthesis of a macrocyclic, tetradentate isocyanide ligand, CN4, and facile coordination to rhodium(I) yielding [Rh(CN4)][BArF4]. Single-crystal X-ray diffraction upon acetone-solution grown crystals reveals formation of a tetrameric RhI stack, constructed of two dimeric forms of monomers. UV–visible absorption spectroscopy shows two prominent absorption bands, assigned to dimer (525 nm) and tetramer (840 nm), confirming stacked species. These assignments are further supported by DOSY measurements. Solvent control over this equilibrium is achieved first with acetonitrile, favoring only tetrameric aggregation, and also with dichloromethane, disabling aggregation completely. Upon excitation, the monomeric form returns to its electronic ground state in less than 10 ns. The near-infrared-absorbing tetramer exhibits an excited state with a lifetime of 150 ns in deaerated acetonitrile and NIR-II emission at 1040 nm. This discovery provides new opportunities for innovation in photophysics and photochemistry through polynuclear architectures that exhibit emergent properties compared to traditional mononuclear transition metal complexes.

Visible photons carry significantly more energy than the thermal energies typically used to overcome activation barriers in conventional chemistry. This thermodynamic advantage enables photochemical reactions that are inaccessible from electronic ground states. However, photochemistry also faces a kinetic challenge: excited states are inherently short-lived, necessitating rapid reactivity before their decay. In this Outlook, we explore the unique interplay of thermodynamics and kinetics in molecular photochemistry. We highlight current limits and knowledge gaps and propose directions for advancing the conceptual framework of photocatalysis. Topics include the design of photocatalysts with extreme redox potentials, the use of solvated electrons and visible-to-UV upconversion, and the potential to bypass Kasha’s rule for higher-energy photochemical processes. Our aim is to survey strategies for pushing the boundaries of photocatalysis and to inspire future conceptual innovation in the field.

Classical upconversion employs sensitizers and annihilators as two distinct molecular species and is, therefore, classified as heteromolecular. Homomolecular upconversion, the unification of both role...

The light-induced separation of charges, fundamental to natural photosynthesis, is key to converting solar energy into chemical energy in artificial systems. One challenge is that charges tend to spon...

RhI dimers with bridging aryl isocyanide and di-phosphine ligands show NIR-I or NIR-II fluorescence/phosphorescence, depending on the ligands and conformational rigidity at the Rh2 core. Rh-Rh intera...

Halogenation of ligands intensely modulates the redox and photophysical properties of transition-metal complexes, yet fully halogenated systems remain largely unexplored. Here we report the synthesis ...

The total spin of a metal center can be switched in different ways. In this concept, the phenomenon spin crossover is compared with coordination-induced spin-state switching. The impact of the switch....

chemistry-europe.onlinelibrary.wiley.com

Transition-metal complexes featuring metal-centered excited states have recently emerged as mechanistically distinct platforms for selective photochemistry, including photoredox catalysis. Among these...

nanoscience.unibas.ch