Photoreduction of Anthracenes Catalyzed by peri-Xanthenoxanthene: a Scalable and Sustainable Birch-Type Alternative.

The typical Birch reduction transforms arenes into cyclohexa-1,4-dienes by using alkali metals, an alcohol as a proton source, and an amine as solvent. Capitalizing on the strong photoreductive properties of peri-xanthenoxanthene (PXX), herein we report the photocatalyzed "Birch-type" reduction of acenes by employing visible blue light irradiation at room temperature in the presence of air. Upon excitation at 405 or 460 nm in the presence of a mixture of N,N-diisopropylethylamine (DIPEA) and trifluoromethanesulfonimide (HNTf2 ) in DMSO, PXX photocatalyzes the selective reduction of full-carbon acene derivatives (24-75 %). Immobilization of PXX onto polydimethylsiloxane (PDMS) beads (PXX-PDMS) allowed the use of the catalyst in heterogeneous batch reactions, giving 9-phenyl-9,10-dihydroanthracene in high yield (68 %). The catalyst could easily be recovered and reused, with no notable drop in performance observed after five reaction cycles. Integration of the PXX-PDMS beads into a microreactor enabled the reduction of acenes under continuous-flow conditions, thereby validating the sustainability and scalability of this heterogeneous-phase approach.

Tweaking the Optoelectronic Properties of S-Doped Polycyclic Aromatic Hydrocarbons by Chemical Oxidation.

Peri-thiaxanthenothiaxanthene, an S-doped analog of peri-xanthenoxanthene, is used as a polycyclic aromatic hydrocarbon (PAH) scaffold to tune the molecular semiconductor properties by editing the oxidation state of the S-atoms. Chemical oxidation of peri-thiaxanthenothiaxanthene with H2 O2 led to the relevant sulfoxide and sulfone congeners, whereas electrooxidation gave access to sulfonium-type derivatives forming crystalline mixed valence (MV) complexes. These complexes depicted peculiar molecular and solid-state arrangements with face-to-face π-π stacking organization. Photophysical studies showed a widening of the optical bandgap upon progressive oxidation of the S-atoms, with the bis-sulfone derivative displaying the largest value (E00 =2.99 eV). While peri-thiaxanthenothiaxanthene showed reversible oxidation properties, the sulfoxide and sulfone derivatives mainly showed reductive events, corroborating their n-type properties. Electric measurements of single crystals of the MV complexes exhibited a semiconducting behavior with a remarkably high conductivity at room temperature (10-1 -10-2  S cm-1 and 10-2 -10-3  S cm-1 for the O and S derivatives, respectively), one of the highest reported so far. Finally, the electroluminescence properties of the complexes were tested in light-emitting electrochemical cells (LECs), obtaining the first S-doped mid-emitting PAH-based LECs.

Solvent-driven chirality for luminescent self-assembled structures: experiments and theory.

We describe, for a single platinum complex bearing a dipeptide moiety, a solvent-driven interconversion from twisted to straight micrometric assembled structures with different chirality. The photophysical and morphological properties of the aggregates have been investigated as well as the role of the media and concentration. A real-time visualization of the solvent-driven interconversion processes has been achieved by confocal microscopy. Finally, atomistic and coarse-grained simulations, providing results consistent with the experimental observations, allow to obtain a molecular-level insight into the interesting solvent-responsive behavior of this system.

Boron-Nitrogen-Doped Nanographenes: A Synthetic Tale from Borazine Precursors.

In this work, a comprehensive account of the authors' synthetic efforts to prepare borazino-doped hexabenzocoronenes by using the Friedel-Crafts-type electrophilic aromatic substitution is reported. Hexafluoro-functionalized aryl borazines, bearing an ortho fluoride leaving group on each of the N- and B-aryl rings, was shown to lead to cascade-type electrophilic aromatic substitution events in the stepwise C-C bond formation, giving higher yields of borazinocoronenes than those obtained with borazine precursors bearing fluoride leaving groups at the ortho positions of the B-aryl substituents. By using this pathway, an unprecedented boroxadizine-doped PAH featuring a gulf-type periphery could be isolated, and its structure proven by single-crystal X-ray diffraction analysis. Mechanistic studies on the stepwise Friedel-Crafts-type cyclization suggest that the mechanism of the planarization reaction proceeds through extension of the π system. To appraise the doping effect of the boroxadizine unit on the optoelectronic properties of topology-equivalent molecular graphenes, the all-carbon and pyrylium PAH analogues, all featuring a gulf-type periphery, were also prepared. As already shown for the borazino-doped hexabenzocoronene, the replacement of the central benzene ring by its B3 N2 O congener widens the HOMO-LUMO gap and dramatically enhances the fluorescence quantum yield.

Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores.

Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.

Oxygen-Doped Zig-Zag Molecular Ribbons.

The synthesis of a zig-zag oxygen-doped molecular rhombic ribbon has been achieved. This includes oxidative C-C and C-O bond formations that allowed the stepwise elongation and planarization of an oxa-congener of 2,7-periacenoacene. X-ray diffraction analysis corroborated the flat structure and the zig-zag topology of the O-doped edges. Photophysical and electrochemical investigations showed that the extension of the peri-xanthenoxanthene (PXX) into the molecular ribbon induces a noticeable shrinking of the molecular band gap devised by a rising of the HOMO energy level, a desirable property for p-type organic semiconductors.

Customizing Photoredox Properties of PXX-based Dyes through Energy Level Rigid Shifts of Frontier Molecular Orbitals.

Here we describe the synthesis of electron-rich PXX derivatives in which the energy levels of the excited states have been rigidly shifted through the insertion of imide groups. This has allowed the development of a new series of oxygen-doped photoredox-active chromophores with improved oxidizing and reducing properties. Capitalizing on the dehalogenation of organic halides as a model reaction, we could investigate the photooxidative and photoreductive potential of these molecules in model chemical transformations. Depending on the substrate, solvent and dye the reaction mechanism can follow different paths. This prompted us to consider the first chemoselective transformation protocol, in which two different C-Br bonds could be chemoselectively reacted through the sequential photoactivation of two different colorants.