A General Platform for Visible Light Sulfonylation Reactions Enabled by Catalytic Triarylamine EDA Complexes.

Catalytic electron donor-acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- and ruthenium-based photoredox synthetic methods. Yet, these complexes remain underexplored and reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report a novel EDA complex employing tris(4-methoxyphenyl) amine as a catalytic donor for the sulfonylation of alkenes using inexpensive and readily available sulfonyl chlorides. Applying this operationally simple, visible-light-mediated general platform, we report both the redox-neutral and net-reductive functionalization of more than 60 substrates, encompassing vinylic or allylic sulfonylation, hydrosulfonylation, and sulfamoylation of activated and unactivated alkenes and alkynes.

Design of Furan-Based Acceptors for Organic Photovoltaics.

We explore a series of furan-based non-fullerene acceptors and report their optoelectronic properties, solid-state packing, photodegradation mechanism and application in photovoltaic devices. Incorporating furan building blocks leads to the expected enhanced backbone planarity, reduced band gap and red-shifted absorption of these acceptors. Still, their position in the molecule is critical for stability and device performance. We found that the photodegradation of these acceptors originates from two distinct pathways: electrocyclic photoisomerization and Diels-Alder cycloaddition of singlet oxygen. These mechanisms are of general significance to most non-fullerene acceptors, and the photostability depends strongly on the molecular structure. Placement of furans next to the acceptor termini leads to better photostability, well-balanced hole/electron transport, and significantly improved device performance. Methylfuran as the linker offers the best photostability and power conversion efficiency (>14 %), outperforming all furan-based acceptors reported to date and all indacenodithiophene-based acceptors. Our findings show the possibility of photostable furan-based alternatives to the currently omnipresent thiophene-based photovoltaic materials.

Thiele's Fluorocarbons: Stable Diradicaloids with Efficient Visible-to-Near-Infrared Fluorescence from a Zwitterionic Excited State.

Thiele's hydrocarbon was the first synthesized diradicaloid in the search for stable open-shell structures, but it remains sensitive to oxygen and light. We here report the synthesis of Thiele's fluorocarbon (TFC) and its derivatives exhibiting exceptional thermal, oxidative, and photostability. TFCs have remarkable luminescent properties with yellow to NIR fluorescence and up to 100% quantum yields. X-ray crystallography and ESR spectroscopy confirm their closed-shell quinoidal ground state. As expected from their symmetric nonpolar structure, the TFCs' absorption spectra show no solvent effect, but their emission reveals an extraordinarily large Stokes shift which increases with solvent polarity (from 0.9 eV in cyclohexane to 1.5 eV in acetonitrile). We show that this behavior is a result of sudden polarization, leading to a zwitterionic excited state.

Efficient room-temperature phosphorescence of covalent organic frameworks through covalent halogen doping.

Organic room-temperature phosphorescence, a spin-forbidden radiative process, has emerged as an interesting but rare phenomenon with multiple potential applications in optoelectronic devices, biosensing and anticounterfeiting. Covalent organic frameworks (COFs) with accessible nanoscale porosity and precisely engineered topology can offer unique benefits in the design of phosphorescent materials, but these are presently unexplored. Here, we report an approach of covalent doping, whereby a COF is synthesized by copolymerization of halogenated and unsubstituted phenyldiboronic acids, allowing for random distribution of functionalized units at varying ratios, yielding highly phosphorescent COFs. Such controlled halogen doping enhances the intersystem crossing while minimizing triplet-triplet annihilation by diluting the phosphors. The rigidity of the COF suppresses vibrational relaxation and allows a high phosphorescence quantum yield (ΦPhos ≤ 29%) at room temperature. The permanent porosity of the COFs and the combination of the singlet and triplet emitting channels enable a highly efficient COF-based oxygen sensor, with an ultra-wide dynamic detection range (~103-10-5 torr of partial oxygen pressure).

Room Temperature Phosphorescence vs Triplet-Triplet Annihilation in N-Substituted Acridone Solids.

Organic room temperature phosphorescent (ORTP) compounds have recently emerged as a promising class of emissive materials with a multitude of potential applications. However, the number of building blocks that give rise to efficient ORTP materials is still limited, and the rules for engineering phosphorescent properties in organic solids are not well understood. Here, we report ORTP in a series of N-substituted acridone derivatives with electron-donating, electron-withdrawing, and sterically bulky substituents. X-ray crystallography shows that the solid-state packing varies progressively between coparallel and antiparallel π-stacking and separated π-dimers, depending on the size of the substituent. The detailed photophysical studies supported by DFT calculations reveal complex dynamics of singlet and triplet excited states, depending on the electronic effects of substituents and solid-state packing. The programmable molecular packing provides a lever to control the triplet-triplet annihilation that is manifested as delayed fluorescence in acridone derivatives with continuous (both parallel and antiparallel) π-stacking.

Examining the role of acceptor molecule structure in self-assembled bilayers: surface loading, stability, energy transfer, and upconverted emission.

Self-assembly of sensitizer and acceptor molecules has recently emerged as a promising strategy to facilitate and harness photon upconversion via triplet-triplet annihilation (TTA-UC). In addition to the energetic requirements, the structure and relative orientation of these molecules can have a strong influence on TTA-UC rates and efficiency. Here we report the synthesis of five different acceptor molecules composed of an anthracene core functionalized with 9,10- or 2,6-phenyl, methyl, or directly bound phosphonic acid groups and their incorporation into self-assembled bilayers on a ZrO2 surface. All five films facilitate green-to-blue photon upconversion with Φuc as high as 0.0023. The efficiency of TTA, and not triplet energy transfer, fluorescence, or losses via FRET, was primarily responsible for dictating the Φuc emission. Even for molecules having similar photophysical properties, variation in the position of the phosphonic acid resulted in dramatically different ΦTTA, Ith values, γTTA, and D. Interestingly, we observed a strong linear correlation between ΦTTA and the Ith value but the cause of this relationship, if any, is unclear.