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Autophagy is a key cellular quality control mechanism. Nutrient stress triggers bulk autophagy, which nonselectively degrades cytoplasmic material upon formation and liquid-liquid phase separation of the autophagy-related gene 1 (Atg1) complex. In contrast, selective autophagy eliminates protein aggregates, damaged organelles and other cargoes that are targeted by an autophagy receptor. Phase separation of cargo has been observed, but its regulation and impact on selective autophagy are poorly understood. Here, we find that key autophagy biogenesis factors phase separate into initiation hubs at cargo surfaces in yeast, subsequently maturing into sites that drive phagophore nucleation. This phase separation is dependent on multivalent, low-affinity interactions between autophagy receptors and cargo, creating a dynamic cargo surface. Notably, high-affinity interactions between autophagy receptors and cargo complexes block initiation hub formation and autophagy progression. Using these principles, we converted the mammalian reovirus nonstructural protein µNS, which accumulates as particles in the yeast cytoplasm that are not degraded, into a neo-cargo that is degraded by selective autophagy. We show that initiation hubs also form on the surface of different cargoes in human cells and are key to establish the connection to the endoplasmic reticulum, where the phagophore assembly site is formed to initiate phagophore biogenesis. Overall, our findings suggest that regulated phase separation underscores the initiation of both bulk and selective autophagy in evolutionarily diverse organisms., Competing Interests: Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

The formation of excited dimer states, so called excimers, is an important phenomenon in many organic molecular semiconductor solid state aggregates. In contrast to Frenkel exciton-polarons, an excimer is long-lived and energetically low-lying due to stabilization resulting from a substantial reorganization of the intermolecular geometry. Here, we show that ultrafast electron diffraction can follow the dynamics of solid-state excimer formation in polycrystalline thin films of a molecular semiconductor, revealing both the key reaction modes and the eventual structure of the emitting state. We study the prototypical organic semiconductor zinc-phthalocyanine (ZnPc) in its crystallographic α -phase as a model excimeric system. We show that the excimer forms in a two-step process starting with a fast dimerization (approx. 0.4 ps) followed by a subsequent slow shear-twist motion (14 ps) leading to an alignment of the π -systems of the involved monomers. This structural distortion persists well beyond 300 ps. Furthermore, we show that while the same excimer geometry is present in partially fluorinated derivatives of ZnPc, the formation kinematics slow down with increasing level of fluorination., Competing Interests: Competing interests statement:The authors declare no competing interest.

Liquid protein condensates produced by phase separation are involved in the spatiotemporal control of cellular functions, while solid fibrous aggregates (amyloids) are associated with diseases and/or manifest as infectious or heritable elements (prions). Relationships between these assemblies are poorly understood. The Saccharomyces cerevisiae release factor Sup35 can produce both fluid liquid-like condensates (e.g., at acidic pH) and amyloids (typically cross-seeded by other prions). We observed acidification-independent formation of Sup35-based liquid condensates in response to hyperosmotic shock in the absence of other prions, both at increased and physiological expression levels. The Sup35 prion domain, Sup35N, is both necessary and sufficient for condensate formation, while the middle domain, Sup35M antagonizes this process. Formation of liquid condensates in response to osmotic stress is conserved within yeast evolution. Notably, condensates of Sup35N/NM protein originated from the distantly related yeast Ogataea methanolica can directly convert to amyloids in osmotically stressed S. cerevisiae cells, providing a unique opportunity for real-time monitoring of condensate-to-fibril transition in vivo by fluorescence microscopy. Thus, cellular fate of stress-induced condensates depends on protein properties and/or intracellular environment., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

The surface molecular doping of organic semiconductors can play an important role in the development of organic electronic or optoelectronic devices. Single-crystal rubrene remains a leading molecular candidate for applications in electronics due to its high hole mobility. In parallel, intensive research into the fabrication of flexible organic electronics requires the careful design of functional interfaces to enable optimal device characteristics. To this end, the present work seeks to understand the effect of surface molecular doping on the electronic band structure of rubrene single crystals. Our angle-resolved photoemission measurements reveal that the Fermi level moves in the band gap of rubrene depending on the direction of surface electron-transfer reactions with the molecular dopants, yet the valence band dispersion remains essentially unperturbed. This indicates that surface electron-transfer doping of a molecular single crystal can effectively modify the near-surface charge density, while retaining good charge-carrier mobility.

Singlet fission 1-13 may boost photovoltaic efficiency 14-16 by transforming a singlet exciton into two triplet excitons and thereby doubling the number of excited charge carriers. The primary step of singlet fission is the ultrafast creation of the correlated triplet pair 17 . Whereas several mechanisms have been proposed to explain this step, none has emerged as a consensus. The challenge lies in tracking the transient excitonic states. Here we use time- and angle-resolved photoemission spectroscopy to observe the primary step of singlet fission in crystalline pentacene. Our results indicate a charge-transfer mediated mechanism with a hybridization of Frenkel and charge-transfer states in the lowest bright singlet exciton. We gained intimate knowledge about the localization and the orbital character of the exciton wave functions recorded in momentum maps. This allowed us to directly compare the localization of singlet and bitriplet excitons and decompose energetically overlapping states on the basis of their orbital character. Orbital- and localization-resolved many-body dynamics promise deep insights into the mechanics governing molecular systems 18-20 and topological materials 21-23 ., (© 2023. The Author(s).)

Stacked organic optoelectronic devices make use of electrode materials with different work functions, leading to efficient large area light emission. In contrast, lateral electrode arrangements offer the possibility to be shaped as resonant optical antennas, radiating light from subwavelength volumes. However, tailoring electronic interface properties of laterally arranged electrodes with nanoscale gaps - to e.g. optimize charge-carrier injection - is rather challenging, yet crucial for further development of highly efficient nanolight sources. Here, we demonstrate site-selective functionalization of laterally arranged micro- and nanoelectrodes by means of different self-assembled monolayers. Upon applying an electric potential across nanoscale gaps, surface-bound molecules are removed selectively from specific electrodes by oxidative desorption. Kelvin-probe force microscopy as well as photoluminescence measurements are employed to verify the success of our approach. Moreover, we obtain asymmetric current-voltage characteristics for metal-organic devices in which just one of the electrodes is coated with 1-octadecanethiol; further demonstrating the potential to tune interface properties of nanoscale objects. Our technique paves the way for laterally arranged optoelectronic devices based on selectively engineered nanoscale interfaces and in principle enables molecular assembly with defined orientation in metallic nano-gaps.

Molecular emitters that combine circularly polarized luminescence (CPL) and high radiative rate constants of the triplet exciton decay are highly attractive for electroluminescent devices (OLEDs) or next-generation photonic applications, such as spintronics, quantum computing, cryptography, or sensors. However, the design of such emitters is a major challenge because the criteria for enhancing these two properties are mutually exclusive. In this contribution, we show that enantiomerically pure {Cu(Cbz R )[( S / R )-BINAP]} [R = H ( 1 ), 3,6- t Bu ( 2 )] are efficient thermally activated delayed fluorescence (TADF) emitters with high radiative rate constants of k TADF up to 3.1 × 10 5 s -1 from 1/3 LLCT states according to our temperature-dependent time-resolved luminescence studies. The efficiency of the TADF process and emission wavelengths are highly sensitive to environmental hydrogen bonding of the ligands, which can be disrupted by grinding of the crystalline materials. The origin of this pronounced mechano-stimulus photophysical behavior is a thermal equilibrium between the 1/3 LLCT states and a 3 LC state of the BINAP ligand, which depends on the relative energetic order of the excited states and is prone to inter-ligand C-H···π interactions. The copper(I) complexes are also efficient CPL emitters displaying exceptional dissymmetry values g lum of up to ±0.6 × 10 -2 in THF solution and ±2.1 × 10 -2 in the solid state. Importantly for application in electroluminescence devices, the C-H···π interactions can also be disrupted by employing sterically bulky matrices. Accordingly, we have investigated various matrix materials for successful implementation of the chiral copper(I) TADF emitters in proof-of-concept CP-OLEDs.

Multi-molecular excited states accompanied by intra- and inter-molecular geometric relaxation are commonly encountered in optical and electrooptical studies and applications of organic semiconductors as, for example, excimers or charge transfer states. Understanding the dynamics of these states is crucial to improve organic devices such as light emitting diodes and solar cells. Their full microscopic description, however, demands sophisticated tools such as ab initio quantum chemical calculations which come at the expense of high computational costs and are prone to errors by assumptions as well as iterative algorithmic procedures. Hence, the analysis of spectroscopic data is often conducted at a phenomenological level only. Here, we present a toolkit to analyze temperature dependent luminescence data and gain first insights into the relevant microscopic parameters of the molecular system at hand. By means of a Franck-Condon based approach considering a single effective inter-molecular vibrational mode and different potentials for the ground and excited state we are able to explain the luminescence spectra of such multi-molecular states. We demonstrate that by applying certain reasonable simplifications the luminescence of charge transfer states as well as excimers can be satisfactorily reproduced for temperatures ranging from cryogenics to above room temperature. We present a semi-classical and a quantum-mechanical description of our model and, for both cases, demonstrate its applicability by analyzing the temperature dependent luminescence of the amorphous donor-acceptor heterojunction tetraphenyldibenzoperiflanthene:C 60 as well as polycrystalline zinc-phthalocyanine to reproduce the luminescence spectra and extract relevant system parameters such as the excimer binding energy.

Molecular near-IR (NIR) triplet-state emitters are of importance for the development of new, organic-electronics-based telecommunication technologies as optical fibers operating in the corresponding spectral bands allow for data transfer over much longer distances due to the significantly lower attenuation. However, achieving such low-energy triplet excited states with good radiative rate constants is very challenging, and studies regarding the single-photon emission of organometallics in this energy range are scarce. We have prepared a series of trigonal Cu I CAAC complexes bearing chelating ligands with O, N, S, and Se donor atoms and studied their photophysical properties in this context. The compounds show weak low-energy absorption in solution between 400 and 500 nm due to mixed Cu → CAAC 1 MLCT/LLCT states, resulting in yellow-green to orange appearance, which we have also correlated to the 15 N NMR resonances of the π-accepting carbene ligand. In the solid state, phosphorescence from dominant 3 (Cu → CAAC) CT states is observed at room temperature. The emission of the complexes is bathochromically shifted in comparison to structurally related linearly coordinated copper(I) CAAC complexes due to structural reorganization in the excited state to a T-shape. For [Cu(dbm)(CAAC Me )], the broad phosphorescence with outstanding λ max = 760 nm tailors out to ca. 1100 nm and leads to its proof-of-concept application as a nonclassical single-photon light source, constituting key functional units for the implementation of tap-proof data transfer.

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2'-yl)- o -carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive 'mixed' state of 1-(pyren-2'-yl)- o -carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Future photonic devices require efficient, multifunctional, electrically driven light sources with directional emission properties and subwavelength dimensions. Electrically driven plasmonic nanoantennas have been demonstrated as enabling technology. Here, we present the concept of a nanoscale organic light-emitting antenna (OLEA) as a color- and directionality-switchable point source. The device consists of laterally arranged electrically contacted gold nanoantennas with their gap filled by the organic semiconductor zinc phthalocyanine (ZnPc). Since ZnPc shows preferred hole conduction in combination with gold, the recombination zone relocates depending on the polarity of the applied voltage and couples selectively to either of the two antennas. Thereby, the emission characteristics of the device also depend on polarity. Contrary to large-area OLEDs where recombination at metal contacts significantly contributes to losses, our ultracompact OLEA structures facilitate efficient radiation into the far-field rendering transparent electrodes obsolete. We envision OLEA structures to serve as wavelength-scale pixels with tunable color and directionality for advanced display applications.