Increased solar-driven chemical transformations through surface-induced benzoperylene aggregation in dye-sensitized photoanodes.

The impact of benzo[ghi]perylenetriimide (BPTI) dye aggregation on the performance of photoelectrochemical devices was explored, through imide-substitution with either alkyl (BPTI-A, 2-ethylpropyl) or bulky aryl (BPTI-B, 2,6-diisopropylphenyl) moieties, to, respectively, enable or suppress aggregation. While both dyes demonstrated similar monomeric optoelectronic properties in solution, adsorption onto mesoporous SnO2 revealed different behavior, with BPTI-A forming aggregates via π-stacking and BPTI-B demonstrating reduced aggregation in the solid state. BPTI photoanodes were tested in dye-sensitized solar cells (DSSCs) before application to dye-sensitized photoelectrochemical cells (DSPECs) for Br2 production (a strong oxidant) coupled to H2 generation (a solar fuel). BPTI-A demonstrated a twofold higher dye loading of the SnO2 surface than BPTI-B, resulting in a fivefold enhancement to both photocurrent and Br2 production. The enhanced output of the photoelectrochemical systems (with respect to dye loading) was attributed to both J- and H- aggregation phenomena in BPTI-A photoanodes that lead to improved light harvesting. Our investigation provides a strategy to exploit self-assembly via aggregation to improve molecular light-harvesting and charge separation properties that can be directly applied to dye-sensitized photoelectrochemical devices.

PhenTAA: A Redox-Active N4-Macrocyclic Ligand Featuring Donor and Acceptor Moieties.

Here, we present the development and characterization of the novel PhenTAA macrocycle as well as a series of [Ni(R2PhenTAA)]n complexes featuring two sites for ligand-centered redox-activity. These differ in the substituent R (R = H, Me, or Ph) and overall charge of the complex n (n = -2, -1, 0, +1, or +2). Electrochemical and spectroscopic techniques (CV, UV/vis-SEC, X-band EPR) reveal that all redox events of the [Ni(R2PhenTAA)] complexes are ligand-based, with accessible ligand charges of -2, -1, 0, +1, and +2. The o-phenylenediamide (OPD) group functions as the electron donor, while the imine moieties act as electron acceptors. The flanking o-aminobenzaldimine groups delocalize spin density in both the oxidized and reduced ligand states. The reduced complexes have different stabilities depending on the substituent R. For R = H, dimerization occurs upon reduction, whereas for R = Me/Ph, the reduced imine groups are stabilized. This also gives electrochemical access to a [Ni(R2PhenTAA)]2- species. DFT and TD-DFT calculations corroborate these findings and further illustrate the unique donor-acceptor properties of the respective OPD and imine moieties. The novel [Ni(R2PhenTAA)] complexes exhibit up to five different ligand-based oxidation states and are electrochemically stable in a range from -2.4 to +1.8 V for the Me/Ph complexes (vs Fc/Fc+).

meta-C-H Arylation of Aniline Derivatives via Palladium/ S,O-Ligand/Norbornene Cooperative Catalysis.

Aromatic amines are ubiquitous moieties in organic molecules and their direct functionalization is of great interest in many research areas due to their prevalence in pharmaceuticals and organic electronics. While several synthetic tools exist for the ortho- and para-functionalization of anilines, the functionalization of the less reactive meta-position is not easy to achieve with current methods. To date, the meta-C-H arylation of aniline derivatives has been restricted to either the use of directing groups & templates, or their transformation into anilides & quaternary anilinium salts. Herein, we report the first general and efficient meta-C-H-arylation of non-directed aniline derivatives via cooperative catalysis with a palladium-S,O-ligand-norbornene system. The reaction proceeds under mild conditions with a wide range of aniline derivatives and aryl iodides, while being operationally simple and scalable. Our preliminary mechanistic investigation-including the isolation of several palladium complexes and deuterium experiments-reveal useful insights into the substituent-effects of both the aniline-substrate and the norbornene-mediator during the meta-C-H activation step.

Rotaxane-Functionalized Dyes for Charge-Rectification in p-Type Photoelectrochemical Devices.

A supramolecular photovoltaic strategy is applied to enhance power conversion efficiencies (PCE) of photoelectrochemical devices by suppressing electron-hole recombination after photoinduced electron transfer (PET). Here, the author exploit supramolecular localization of the redox mediator-in close proximity to the dye-through a rotaxane topology, reducing electron-hole recombination in p-type dye-sensitized solar cells (p-DSSCs). Dye PRotaxane features 1,5-dioxynaphthalene recognition sites (DNP-arms) with a mechanically-interlocked macrocyclic redox mediator naphthalene diimide macrocycle (3-NDI-ring), stoppering synthetically via click chemistry. The control molecule PStopper has stoppered DNP-arms, preventing rotaxane formation with the 3-NDI-ring. Transient absorption and time-resolved fluorescence spectroscopy studies show ultrafast (211 ± 7 fs and 2.92 ± 0.05 ps) PET from the dye-moiety of PRotaxane to its mechanically interlocked 3-NDI-ring-acceptor, slowing down the electron-hole recombination on NiO surfaces compared to the analogue . p-DSSCs employing PRotaxane (PCE = 0.07%) demonstrate a 30% PCE increase compared to PStopper (PCE = 0.05%) devices, combining enhancements in both open-circuit voltages (VOC = 0.43 vs 0.36 V) and short-circuit photocurrent density (JSC = -0.39 vs -0.34 mA cm-2 ). Electrochemical impedance spectroscopy shows that PRotaxane devices exhibit hole lifetimes (τh ) approaching 1 s, a 16-fold improvement compared to traditional I- /I3 - -based systems (τh = 50 ms), demonstrating the benefits obtained upon nanoengineering of interfacial dye-regeneration at the photocathode.

Pd12MnL24 (for n = 6, 8, 12) nanospheres by post-assembly modification of Pd12L24 spheres.

In this contribution, we describe a post-assembly modification approach to selectively coordinate transition metals in Pd12L24 cuboctahedra. The herein reported approach involves the preparation of Pd12L24 nanospheres with protonated nitrogen donor ligands that are covalently linked at the interior. The so obtained Pd12(LH+)24 nanospheres are shown to be suitable for coordinative post-modification after deprotection by deprotonation. Selective formation of tetra-coordinated MB in Pd12MB6L24, tri-coordinated MB in Pd12MB8L24 nanospheres and two-coordinated MB in Pd12MB12L24 nanospheres is achieved as a result of different nitrogen donor ligands. A combination of pulsed EPR spectroscopy (DEER) to measure Cu-Cu distances in the different spheres, NMR studies and computational investigations, support the presence of the complexes at precise locations of the Pd12MB6L24 nanosphere. The general post-assembly modification methodology can be extended using other transition metal precursors or supramolecular systems and can guide precise formation and investigation of novel transition metal-complex containing nanospheres with well-defined composition.

Homolytic C-H Bond Activation by Phosphine-Quinone-Based Radical Ion Pairs.

Herein, we present the formation of transient radical ion pairs (RIPs) by single-electron transfer (SET) in phosphine-quinone systems and explore their potential for the activation of C-H bonds. PMes3 (Mes=2,4,6-Me3 C6 H2 ) reacts with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) with formation of the P-O bonded zwitterionic adduct Mes3 P-DDQ (1), while the reaction with the sterically more crowded PTip3 (Tip=2,4,6-iPr3 C6 H2 ) afforded C-H bond activation product Tip2 P(H)(2-[CMe2 (DDQ)]-4,6-iPr2 -C6 H2 ) (2). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip3 ]⋅+ [DDQ]⋅- , and subsequent homolytic C-H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip2 P(H)(2-[CMe2 {TCQ-B(C6 F5 )3 }]-4,6-iPr2 -C6 H2 ) (4, TCQ=tetrachloro-1,4-benzoquinone) and Tip2 P(H)(2-[CMe2 {oQtBu -B(C6 F5 )3 }]-4,6-iPr2 -C6 H2 ) (8, oQtBu =3,5-di-tert-butyl-1,2-benzoquinone), from reactions of PTip3 with Lewis-acid activated quinones, TCQ-B(C6 F5 )3 and oQtBu -B(C6 F5 )3 , respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C-H bond activation by the synergistic action of radical ion pairs.

Thermal/Blue Light Induced Cross-Linking of Acrylic Coatings with Diazo Compounds.

The thermal curing of industrial coatings (e.g., car painting and metal coil coatings) is accompanied by a substantial energy consumption due to the intrinsically high temperatures required during the curing process. Therefore, the development of new photochemical curing processes-preferably using visible light-is in high demand. This work describes new diazo-based cross-linkers that can be used to photocure acrylic coatings using blue light. This work demonstrates that the structure of the tethered diazo compounds influences the cross-linking efficiency, finding that side reactions are suppressed upon engineering greater molecular flexibility. Importantly, this work shows that these diazo compounds can be employed as either thermal or photochemical cross-linkers, exhibiting identical crosslinking performances. The performance of diazo-cross-linked coatings is evaluated to reveal excellent water resistance and demonstrably similar material properties to UV-cured acrylates. These studies pave the way for further usage of diazo-functionalized cross-linkers in the curing of paints and coatings.

In vivo biodistribution of kinetically stable Pt2L4 nanospheres that show anti-cancer activity.

There is an increasing interest in the application of metal-organic cages (MOCs) in a biomedicinal context, as they can offer non-classical distribution in organisms compared to molecular substrates, while revealing novel cytotoxicity mechanisms. Unfortunately, many MOCs are not sufficiently stable under in vivo conditions, making it difficult to study their structure-activity relationships in living cells. As such, it is currently unclear whether MOC cytotoxicity stems from supramolecular features or their decomposition products. Herein, we describe the toxicity and photophysical properties of highly-stable rhodamine functionalized platinum-based Pt2L4 nanospheres as well as their building blocks under in vitro and in vivo conditions. We show that in both zebrafish and human cancer cell lines, the Pt2L4 nanospheres demonstrate reduced cytotoxicity and altered biodistribution within the body of zebrafish embryos compared to the building blocks. We anticipate that the composition-dependent biodistribution of Pt2L4 spheres together with their cytotoxic and photophysical properties provides the fundament for MOC application in cancer therapy.

The role of Pb oxidation state of the precursor in the formation of 2D perovskite microplates.

Two-dimensional (2D) lead halide perovskites are an exciting class of materials currently being extensively explored for photovoltaics and other optoelectronic applications. Their ionic nature makes them ideal candidates for solution processing into both thin films and nanostructured crystals. Understanding how 2D lead halide perovskite crystals form is key towards full control over their physical properties, which may enable new physical phenomena and devices. Here, we investigate the effects of the Pb oxidation state of the initial inorganic precursor on the growth of pure-phase (n = 1) - Popper 2D perovskite BA2PbI4 in single-step synthesis. We examine the different crystallisation routes in exposing PbO2 and PbI2 powders to a BAI : IPA organo-halide solution, by combining in situ optical microscopy, UV-VIS spectroscopy and time-resolved high performance liquid chromatography. So far, works using PbO2 to synthesise 3D LHPs introduce a preceding step to reduce PbO2 into either PbO or PbI2. In this work, we find that BA2PbI4 is directly formed when exposing PbO2 to BAI : IPA without the need for an external reducing agent. We explain this phenomenon by the spontaneous reduction/oxidation of PbO2/BAI that occurs under iodine-rich conditions. We observe differences in the final morphology (rectangles vs. octagons) and nanocrystal growth rate, which we explain through the different chemistry and iodoplumbate complexes involved in each case. As such, this work spans the horizon of usable lead precursors and offers a new turning knob to control crystal growth in single-step LHP synthesis.

Exposing Mechanisms for Defect Clearance in Supramolecular Self-Assembly: Palladium-Pyridine Coordination Revisited.

Spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands are a mainstay of supramolecular chemistry with demonstrated catalytic and optoelectronic applications. The widely reported self-assembly of these palladium-based cages exhibits sensitivity to the solvents, reagents, and/or reactants employed. This sensitivity, and the resulting inconsistency between synthetic protocols, hinders the development of desirable palladium-based cages. We have found that pyridyl ligand substitution─the rate-limiting step of self-assembly─is facilitated by endogenous supporting ligands derived from the solvents, reagents, and reactants employed in synthetic protocols of palladium- and platinum-based assemblies. Here, we present a systematic investigation combining 1H-NMR, electrospray ionization mass spectrometry (ESI─MS), and absorption spectroscopy to characterize the intermediates to support the mechanism of pyridyl ligand substitution on a model complex, M(py)2 (M = (N,N,N',N'-tetramethylethylenediamine)palladium(II), py = pyridine), under simulated synthetic conditions for self-assembly. Our investigation exposes mechanisms for pyridyl ligand substitution, featuring intermediates stabilized by solvent, anion, or (in situ formed) alkoxide moieties. Interrogation of destabilizing agents (2,2,2-trifluoroethanol and tetra(n-butyl)ammonium chloride) reveal similar mechanisms that ultimately facilitate the self-assembly of coordination cages. These findings rationalize widely reported solvent and anion effects in the self-assembly of coordination cages (and similar constructs) while highlighting methodologies to understand the role of supporting ligands in coordination chemistry.

Effector Regulated Catalytic Cyclization of Alkynoic Acids Using Pt2 L4 Cages.

Metabolic pathways are highly regulated by effector molecules that influences the rate of enzymatic reactions. Inspired by the catalytic regulation found in living cells, we report a Pt2 L4 cage of which the activity can be controlled by effectors that bind inside the cage. The cage shows catalytic activity in the lactonization of alkynoic acids, with the reaction rates dependent on the effector guest bound in the cage. Some effector guests enhance the rate of the lactonization by up to 19-fold, whereas one decreases it by 5-fold. When mixtures of specific substrates are used, both starting materials and products act as guests for the Pt2 L4 cage, enhancing its catalytic activity for one substrate while reducing its activity for the other. The reported regulatory behavior obtained by the addition of effector molecules paves the way to the development of more complex, metabolic-like catalyst systems.

Chirality-Driven Self-Assembly of Discrete, Homochiral FeII 2 L3 Cages.

Coordination chemistry is a powerful method to synthesize supramolecular cages with distinct features that suit specific applications. This work demonstrates the synthesis of discrete, homochiral FeII 2 L3 cages via chirality-driven self-assembly. Specifically, the installation of chirality - at both the vertices and ligand backbones - allows the formation of discrete, homochiral FeII 2 L3 cages of different sizes via stereochemical control of the iron(II) centers. We observed that larger cages require multiple chiral centra (chiral ligands and vertices). In contrast, the formation of smaller cages is stereoselective with solely chiral ligands. The latter cages can also be formed from two chiral subcomponents, but only when they have matching chirality. Single-crystal X-ray diffraction of these smaller FeII 2 L3 cages revealed several non-covalent interactions as a driving force for narcissistic chiral self-sorting. This expected behavior was confirmed utilizing the shorter ligands in racemic form, yielding discrete, homochiral FeII 2 L3 cages formed in enantiomeric pairs.

Thermal and (Thermo-Reversible) Photochemical Cycloisomerization of 1H-2-Benzo[c]oxocins: From Synthetic Applications to the Development of a New T-Type Molecular Photoswitch.

A novel T-type molecular photoswitch based on the reversible cyclization of 1H-2-benzo[c]oxocins to dihydro-4H-cyclobuta[c]isochromenes has been developed. The switching mechanism involves a light-triggered ring-contraction of 8-membered 1H-2-benzo[c]oxocins to 4,6-fused O-heterocyclic dihydro-4H-cyclobuta[c]isochromene ring systems, with reversion back to the 1H-2-benzo[c]oxocin state accessible through heating. Both processes are unidirectional and proceed with good efficiency, with switching properties─including reversibility and half-life time─easily adjusted via structural functionalization. Our new molecular-switching platform exhibits independence from solvent polarity, originating from its neutral-charge switching mechanism, a property highly sought-after for biological applications. The photoinduced ring-contraction involves a [2+2] conjugated-diene cyclization that obeys the Woodward-Hoffmann rules. In contrast, the reverse process initiates via a thermal ring-opening (T > 60 °C) to produce the original 8-membered 1H-2-benzo[c]oxocins, which is thermally forbidden according to the Woodward-Hoffmann rules. The thermal ring-opening is likely to proceed via an ortho-quinodimethane (o-QDM) intermediate, and the corresponding switching mechanisms are supported by experimental observations and density functional theory calculations. Other transformations of 1H-2-benzo[c]oxocins were found upon altering reaction conditions: prolonged heating of the 1H-2-benzo[c]oxocins at a significantly elevated temperature (72 h at 120 °C), with the resulting dihydronaphthalenes formed via the o-QDM intermediate. These reactions also proceed with good chemoselectivities, providing new synthetic protocols for motifs found in several bioactive molecules, but are otherwise difficult to access.

Intra-Abdominal Actinomycosis: An Indolent Masquerader of Malignancy.

This report describes the case of a 54-year-old female who presented with the constitutional symptoms of lethargy, weight loss, and asthenia. She had been extensively investigated for possible gynaecological malignancy but with no definitive outcome achieved. The symptoms were persistent and, partly due to occurring during the coronavirus disease 2019 (COVID-19) pandemic, a decision was made to progress with surgical management. Following an oncology multidisciplinary meeting, a decision was made for a total abdominal hysterectomy and bilateral salpingo-oophorectomy. Intra-operatively, there was an incidental finding of an extensive tumour infiltrating the liver, colon, anterior abdominal wall and urinary bladder. A surgical resection with ileostomy was performed on suspicion of an underlying malignancy. Unexpectedly, the histopathological diagnosis revealed actinomycosis. Following this discovery, our entire management plan was altered, and the patient was treated with a prolonged course of antibiotics and recovered well.

Isocyanate-Free Polyurea Synthesis via Ru-Catalyzed Carbene Insertion into the N-H Bonds of Urea.

Polyureas have widespread applications due to their unique material properties. Because of the toxicity of isocyanates, sustainable isocyanate-free routes to prepare polyureas are a field of active research. Current routes to isocyanate-free polyureas focus on constructing the urea moiety in the final polymerizing step. In this study we present a new isocyanate-free method to produce polyureas by Ru-catalyzed carbene insertion into the N-H bonds of urea itself in combination with a series of bis-diazo compounds as carbene precursors. The mechanism was investigated by kinetics and DFT studies, revealing the rate-determining step to be nucleophilic attack on a Ru-carbene moiety by urea. This study paves the way to use transition-metal-catalyzed reactions in alternative routes to polyureas.

S,O-Ligand Promoted meta-C-H Arylation of Anisole Derivatives via Palladium/Norbornene Catalysis.

Reversing the conventional site-selectivity of C-H activation processes provides new retrosynthetic disconnections to otherwise unreactive bonds. Here, we report a new catalytic system based on palladium/norbornene and an S,O-ligand for the meta-C-H arylation of aryl ethers that significantly outperforms previously reported systems. We demonstrate the unique ability of this system to employ alkoxyarene substrates bearing electron donating and withdrawing substituents. Additionally, ortho-substituted aryl ethers are well tolerated, overcoming the "ortho constraint", which is the necessity to have a meta-substituent on the alkoxyarene to achieve high reaction efficiency, by enlisting novel norbornene mediators. Remarkably, for the first time the monoarylation of alkoxyarenes is achieved efficiently enabling the subsequent introduction of a second, different aryl coupling partner to rapidly furnish unsymmetrical terphenyls. Further insight into the reaction mechanism was achieved by isolation and characterization of some Pd-complexes-before and after meta C-H activation-prior to evaluation of their respective catalytic activities.

Cobalt(II)-tetraphenylporphyrin-catalysed carbene transfer from acceptor-acceptor iodonium ylides via N-enolate-carbene radicals.

Square-planar cobalt(II) systems have emerged as powerful carbene transfer catalysts for the synthesis of numerous (hetero)cyclic compounds via cobalt(III)-carbene radical intermediates. Spectroscopic detection and characterization of reactive carbene radical intermediates is limited to a few scattered experiments, centered around monosubstituted carbenes. Here, we reveal the formation of disubstituted cobalt(III)-carbene radicals derived from a cobalt(II)-tetraphenylporphyrin complex and acceptor-acceptor λ3-iodaneylidenes (iodonium ylides) as carbene precursors and their catalytic application. Iodonium ylides generate biscarbenoid species via reversible ligand modification of the paramagnetic cobalt(II)-tetraphenylporphyrin complex catalyst. Two interconnected catalytic cycles are involved in the overall mechanism, with a monocarbene radical and an N-enolate-carbene radical intermediate at the heart of each respective cycle. Notably, N-enolate formation is not a deactivation pathway but a reversible process, enabling transfer of two carbene moieties from a single N-enolate-carbene radical intermediate. The findings are supported by extensive experimental and computational studies.

Aqueous Biphasic Dye-Sensitized Photosynthesis Cells for TEMPO-Based Oxidation of Glycerol.

This work reports an aqueous dye-sensitized photoelectrochemical cell (DSPEC) capable of oxidizing glycerol (an archetypical biobased compound) coupled with H2 production. We employed a mesoporous TiO2 photoanode sensitized with the high potential thienopyrroledione-based dye AP11, encased in an acetonitrile-based redox-gel that protects the photoanode from degradation by aqueous electrolytes. The use of the gel creates a biphasic system with an interface at the organic (gel) electrode and aqueous anolyte. Embedded in the acetonitrile gel is 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), acting as both a redox-mediator and a catalyst for oxidative transformations. Upon oxidation of TEMPO by the photoexcited dye, the in situ generated TEMPO+ shuttles through the gel to the acetonitrile-aqueous interface, where it acts as an oxidant for the selective conversion of glycerol to glyceraldehyde. The introduction of the redox-gel layer affords a 10-fold increase in the conversion of glycerol compared to the purely aqueous system. Our redox-gel protected photoanode yielded a stable photocurrent over 48 hours of continuous operation, demonstrating that this DSPEC is compatible with alkaline aqueous reactions.

Catalytic Synthesis of 1H-2-Benzoxocins: Cobalt(III)-Carbene Radical Approach to 8-Membered Heterocyclic Enol Ethers.

The metallo-radical activation of ortho-allylcarbonyl-aryl N-arylsulfonylhydrazones with the paramagnetic cobalt(II) porphyrin catalyst [CoII(TPP)] (TPP = tetraphenylporphyrin) provides an efficient and powerful method for the synthesis of novel 8-membered heterocyclic enol ethers. The synthetic protocol is versatile and practical and enables the synthesis of a wide range of unique 1H-2-benzoxocins in high yields. The catalytic cyclization reactions proceed with excellent chemoselectivities, have a high functional group tolerance, and provide several opportunities for the synthesis of new bioactive compounds. The reactions are shown to proceed via cobalt(III)-carbene radical intermediates, which are involved in intramolecular hydrogen transfer (HAT) from the allylic position to the carbene radical, followed by a near-barrierless radical rebound step in the coordination sphere of cobalt. The proposed mechanism is supported by experimental observations, density functional theory (DFT) calculations, and spin trapping experiments.

Just Add Water: Modulating the Structure-Derived Acidity of Catalytic Hexameric Resorcinarene Capsules.

The hexameric undecyl-resorcin[4]arene capsule (C11R6) features eight discrete structural water molecules located at the vertices of its cubic suprastructure. Combining NMR spectroscopy with classical molecular dynamics (MD), we identified and characterized two distinct species of this capsule, C11R6-A and C11R6-B, respectively featuring 8 and 15 water molecules incorporated into their respective hydrogen-bonded networks. Furthermore, we found that the ratio of the C11R6-A and C11R6-B found in solution can be modulated by controlling the water content of the sample. The importance of this supramolecular modulation in C11R6 capsules is highlighted by its ability to perform acid-catalyzed transformations, which is an emergent property arising from the hydrogen bonding within the suprastructure. We show that the conversion of C11R6-A to C11R6-B enhances the catalytic rate of a model Diels-Alder cyclization by 10-fold, demonstrating the cofactor-derived control of a supramolecular catalytic process that emulates natural enzymatic systems.