A Dibenzotetrathiafulvalene-Bridged Bis(alkenylruthenium) Complex and Its One- and Two-Electron-Oxidized Forms.

We report on the synthesis of the new bis(alkenylruthenium) complex DBTTF-(ViRu)2 with a longitudinally extended, π-conjugated dibenzotetrathiafulvalene (DBTTF) bridge, characterized by multinuclear NMR, IR, and UV/vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. Cyclic and square-wave voltammetry revealed that DBTTF-(ViRu)2 undergoes four consecutive oxidations. IR, UV/vis/near-IR, and electron paramagnetic resonance spectroscopy indicate that the first oxidation involves the redox-noninnocent DBTTF bridge, while the second oxidation is biased toward one of the peripheral styrylruthenium entities, thereby generating an electronically coupled mixed-valent state ({Ru}-CH═CH)•+-DBTTF•+-(CH═CH-{Ru}) [{Ru} = Ru(CO)Cl(PiPr3)2]. The latter is apparently in resonance with the ({Ru}-CH═CH)•+-DBTTF-(CH═CH-{Ru})•+ and ({Ru}-CH═CH)-DBTTF2+-(CH═CH-{Ru}) forms, which are calculated to lie within 19 kJ/mol. Higher oxidized forms proved too unstable for further characterization. The reaction of DBTTF-(ViRu)2 with the strong organic acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetracyano-p-benzoquinodimethane (TCNQ), and F4TCNQ resulted in formation of the DBTTF-(ViRu)2•+ radical cation, as shown by various spectroscopic techniques. Solid samples of these compounds were found to be highly amorphous and electrically insulating.

Urethane functions can reduce metal salts under hydrothermal conditions: synthesis of noble metal nanoparticles on flexible sponges applied in semi-automated organic reduction.

We report an additive-free one-pot hydrothermal synthesis of Au, Ag, Pd, and alloy AuPd nanoparticles (NPs) anchored on commercial polyurethane (PU) foams. While unable to reduce the precursor metal salts at room temperature, PU is able to serve as a reducing agent under hydrothermal conditions. The resulting NP@PU sponge materials perform comparably to reported state-of-the-art reduction catalysts, and are additionally very well suited for use in semi-automated synthesis: the NP anchoring is strong enough and the support flexible enough to be used as a 'catalytic sponge' that can be manipulated with a robotic arm, i.e., be repeatedly dipped into and drawn out of solutions, wrung out, and re-soaked.

Dual redox-active porous polyimides as high performance and versatile electrode material for next-generation batteries.

Energy storage will be a primordial actor of the ecological transition initiated in the energy and transport sectors. As such, innovative approaches to design high-performance electrode materials are crucial for the development of the next generation of batteries. Herein, a novel dual redox-active and porous polyimide network (MTA-MPT), based on mellitic trianhydride (MTA) and 3,7-diamino-N-methylphenothiazine (MPT) monomers, is proposed for applications in both high energy density lithium batteries and symmetric all-organic batteries. The MTA-MPT porous polyimide was synthesized using a novel environmentally-friendly hydrothermal polymerization method. Rooted in its dual redox proprieties, the MTA-MPT porous polyimide exhibits a high theoretical capacity making it a very attractive cathode material for high energy density battery applications. The cycling performance of this novel electrode material was assessed in both high energy density lithium batteries and light-weight symmetric all-organic batteries, displaying excellent rate capability and long-term cycling stability.

Green hydrothermal synthesis yields perylenebisimide-SiO2 hybrid materials with solution-like fluorescence and photoredox activity.

In organic-inorganic hybrid materials' (HMs) synthesis, it is intrinsically challenging to, at the same time, achieve (i) the concomitant synthesis of the components, (ii) nanoscopic interpenetration of the components, and (iii) covalent linking of the components. We here report the one-pot hydrothermal synthesis (HTS) of inorganic-organic HMs consisting of perylene bisimide (PBI) dyes and silica, using nothing but water as the medium and directly from the corresponding bisanhydrides, n-alkyl amines, and alkoxysilane precursors. First, in the absence of a functionalized alkoxysilane for linking, a mixture of the products, PBI and SiO2, is obtained. This evinces that the two products can be synthesized in parallel in the same vessel. Except for minor micromorphological changes, the concomitant synthesis does not affect each component's physicochemical properties. The PBI/SiO2 mixtures do not show synergistic properties. Second, through adding the linker aminopropyltriethoxysilane (APTS), covalently-linked class II hybrids are obtained. These PBI@SiO2 class II hybrids show synergistic materials properties: increased thermal stability is obtained in combination with nanoscopic homogeneity. The PBI moieties are dissolved in the solid SiO2 matrix, while being covalently linked to the matrix. This leads to solution-like fluorescence with vibronic fine-structure of the dyes. Moreover, through tuning the SiO2 amount, the band gaps of the class II hybrid materials can be systematically shifted. We exploit these optoelectronic properties by using the PBI@SiO2 hybrids as heterogeneous and reusable photoredox catalysts for the reduction of aryl halides. Finally, we present a detailed small-angle X-ray scattering and powder X-ray diffraction study of PBI@SiO2 synthesized at various reaction times, revealing the existence of an ordered PBI-oligomeric silesquioxane-type intermediate, which subsequently further condenses to the final nanoscopically homogeneous PBI@SiO2 material. These ordered intermediates point at HTS' propensity to favor crystallinity (to date known for organic and inorganic compounds, respectively) to also apply to hybrid structures, and shed additional light on the long-standing question of structure formation in the early stages of sol-gel processes: they corroborate Brown's hypothesis (1965) that trifunctional hydroxysilanes form surprisingly well controlled oligomers in the early stages of polycondensation.

Clickable Cisplatin Derivatives as Versatile Tools to Probe the DNA Damage Response to Chemotherapy.

Cisplatin induces DNA crosslinks that are highly cytotoxic. Hence, platinum complexes are frequently used in the treatment of a broad range of cancers. Efficiency of cisplatin treatment is limited by the tumor-specific DNA damage response to the generated lesions. We reasoned that better tools to investigate the repair of DNA crosslinks induced by cisplatin would therefore be highly useful in addressing drug limitations. Here, we synthesized a series of cisplatin derivatives that are compatible with click chemistry, thus allowing visualization and isolation of DNA-platinum crosslinks from cells to study cellular responses. We prioritized one alkyne and one azide Pt(II) derivative, Pt-alkyne-53 and Pt-azide-64, for further biological characterization. We demonstrate that both compounds bind DNA and generate DNA lesions and that the viability of treated cells depends on the active DNA repair machinery. We also show that the compounds are clickable with both a fluorescent probe as well as biotin, thus they can be visualized in cells, and their ability to induce crosslinks in genomic DNA can be quantified. Finally, we show that Pt-alkyne-53 can be used to identify DNA repair proteins that bind within its proximity to facilitate its removal from DNA. The compounds we report here can be used as valuable experimental tools to investigate the DNA damage response to platinum complexes and hence might shed light on mechanisms of chemoresistance.

Siloxane-Based Main-Chain Poly(ionic liquid)s via a Debus-Radziszewski Reaction.

Herein, we synthesized a series of siloxane-based poly(ionic liquid)s (PILs) with imidazolium-type species in the main chain via the multicomponent Debus-Radziszewski reaction. We employed oligodimethylsiloxane diamine precursors to integrate flexible spacers in the polymer backbone and ultimately succeeded in obtaining main-chain PILs with low glass transition temperatures (T g s) in the range of -40 to -18 °C. Such PILs were combined with conventional hydrophobic vinylimidazolium-based PILs for the fabrication of porous membranes via interpolyelectrolyte complexation with poly(acrylic acid), which leads to enhanced mechanical performance in the tensile testing measurements. This study will enrich the structure library of main-chain PILs and open up more opportunities for potential industrial applications of porous imidazolium-based membranes.

Hydrothermal polymerization of porous aromatic polyimide networks and machine learning-assisted computational morphology evolution interpretation.

We report on the hydrothermal polymerization (HTP) of polyimide (PI) networks using the medium H2O and the comonomers 1,3,5-tris(4-aminophenyl)benzene (TAPB) and pyromellitic acid (PMA). Full condensation is obtained at minimal reaction times of only 2 h at 200 °C. The PI networks are obtained as monoliths and feature thermal stabilities of >500 °C, and in several cases even up to 595 °C. The monoliths are built up by networks of densely packed, near-monodisperse spherical particles and annealed microfibers, and show three types of porosity: (i) intrinsic inter-segment ultramicroporosity (<0.8 nm) of the PI networks composing the particles (∼3-5 µm), (ii) interstitial voids between the particles (0.1-2 µm), and (iii) monolith cell porosity (∽10-100 µm), as studied via low pressure gas physisorption and Hg intrusion porosimetry analyses. This unique hierarchical porosity generates an outstandingly high specific pore volume of 7250 mm3 g-1. A large-scale micromorphological study screening the reaction parameters time, temperature, and the absence/presence of the additive acetic acid was performed. Through expert interpretation of hundreds of scanning electron microscopy (SEM) images of the products of these experiments, we devise a hypothesis for morphology formation and evolution: a monomer salt is initially formed and subsequently transformed to overall eight different fiber, pearl chain, and spherical morphologies, composed of PI and, at long reaction times (>48 h), also PI/SiO2 hybrids that form through reaction with the reaction vessel. Moreover, we have developed a computational image analysis pipeline that deciphers the complex morphologies of these SEM images automatically and also allows for formulating a hypothesis of morphology development in HTP that is in good agreement with the manual morphology analysis. Finally, we upscaled the HTP of PI(TAPB-PMA) and processed the resulting powder into dense cylindrical specimen by green solvent-free warm-pressing, showing that one can follow the full route from the synthesis of these PI networks to a final material without employing harmful solvents.

Green Hydrothermal Synthesis of Fluorescent 2,3-Diarylquinoxalines and Large-Scale Computational Comparison to Existing Alternatives.

Invited for this month's cover is the group of Miriam Unterlass at the Technische Universität Wien and the CeMM Research Center for Molecular Medicine of the Austrian Academy of Sciences. The image illustrates the synthesis of quinoxalines in "hot water" and the large-scale computational comparison of all existing syntheses of these quinoxalines. The Full Paper itself is available at 10.1002/cssc.202100433.

Green Hydrothermal Synthesis of Fluorescent 2,3-Diarylquinoxalines and Large-Scale Computational Comparison to Existing Alternatives.

Here, the hydrothermal synthesis (HTS) of 2,3-diarylquinoxalines from 1,2-diketones and o-phenylendiamines (o-PDAs) was achieved. The synthesis is simple, fast, and generates high yields, without requiring any organic solvents, strong acids or toxic catalysts. Reaction times down to <10 min without decrease in yield could be achieved through adding acetic acid as promoter, even for highly apolar biquinoxalines (yield >90 % in all cases). Moreover, it was shown that HTS has high compatibility: (i) hydrochlorides, a standard commercial form of amines, could be used directly as combined amine source and acidic catalyst, and (ii) Boc-diprotected o-PDA could be directly employed as substrate that underwent HT deprotection. A systematic large-scale computational comparison of all reported syntheses of the presented quinoxalines from the same starting compounds showed that this method is more environmentally friendly and less toxic than all existing methods and revealed generic synthetic routes for improving reaction yields. Finally, the application of the synthesized compounds as fluorescent dyes for cell staining was explored.

Biogenic Metal Oxides.

Biogenic metal oxides (MxOy) feature structures as highly functional and unique as the organisms generating them. They have caught the attention of scientists for the development of novel materials by biomimicry. In order to understand how biogenic MxOy could inspire novel technologies, we have reviewed examples of all biogenic MxOy, as well as the current state of understanding of the interactions between the inorganic MxOy and the biological matter they originate from and are connected to. In this review, we first summarize the origins of the precursors that living nature converts into MxOy. From the point-of-view of our materials chemists, we present an overview of the biogenesis of silica, iron and manganese oxides, as the only reported biogenic MxOy to date. These MxOy are found across all five kingdoms (bacteria, protoctista, fungi, plants and animals). We discuss the key molecules involved in the biosynthesis of MxOy, the functionality of the MxOy structures, and the techniques by which the biogenic MxOy can be studied. We close by outlining the biomimetic approaches inspired by biogenic MxOy materials and their challenges, and we point at promising directions for future organic-inorganic materials and their synthesis.

Hydrothermal Generation of Conjugated Polymers Using the Example of Pyrrone Polymers and Polybenzimidazoles.

Various polyimides and polyamides have recently been prepared via hydrothermal synthesis in nothing but H2 O under high-pressure and high-temperature conditions. However, none of the prepared polymers feature a truly conjugated polymer backbone. Here, we report on an expansion of the synthetic scope of this straightforward and inherently environmentally friendly polymerization technique to the generation of conjugated polymers. Selected representatives of two different polymer classes, pyrrone polymers and polybenzimidazoles, were generated hydrothermally. We present a mechanistic discussion of the polymer formation process as well as an electrochemical characterization of the most promising product.

A Diverse View of Science to Catalyse Change.

Valuing diversity leads to scientific excellence, the progress of science and most importantly, it is simply the right thing to do. We can value diversity not only in words, but also in actions.

Acid Free Oxidation and Simple Dispersion Method of MWCNT for High-Performance CFRP.

Carbon nanotubes (CNT) provide an outstanding property spectrum which can be used to improve a wide range of materials. However, the transfer of properties from the nanoscale to a macroscopic material is a limiting factor. Different approaches of functionalizing the surface of a CNT can improve the interaction with the surrounding matrix but is connected to difficult and expensive treatments, which are usually inconvenient for industrial applications. Here, a simple and eco-friendly method is presented for the oxidation of CNT, where hydrogen peroxide (H2O2) is the only chemical needed and no toxic emissions are released. Also, the extensive step of the incorporation of CNT to an epoxy matrix is simplified to an ultrasonic dispersion in the liquid hardener component. The effectiveness is proven by mechanical tests of produced CNT/CFRP and compared to a conventional processing route. The combination of those simple and cost efficient strategies can be utilized to produce multiscale composites with improved mechanical performance in an ecological and economical way.

Green and Rapid Hydrothermal Crystallization and Synthesis of Fully Conjugated Aromatic Compounds.

Highly fused, fully conjugated aromatic compounds are interesting candidates for organic electronics. With higher crystallinity their electronic properties improve. It is shown here that the crystallization of three archetypes of such molecules-pentacenetetrone, indigo, and perinone-can be achieved hydrothermally. Given their molecular structure, this is a truly startling finding. In addition, it is demonstrated that perinone can also be synthesized in solely high-temperature water from the starting compounds naphthalene bisanhydride and o-phenylene diamine without the need for co-solvents or catalysts. The transformation can be drastically accelerated by the application of microwave irradiation. This is the first report on the hydrothermal generation of two fused heterocycles.

Hot Water Generates Crystalline Organic Materials.

In hot water: Hydrothermal crystallization was recently used to transform amporphous polymer networks into amide-linked, stable covalent-organic frameworks. This work is highlighted in the context of the synthesis and especially crystallization of organic materials by using high-temperature water.

Dicyano- and tetracyanopentacene: foundation of an intriguing new class of easy-to-synthesize organic semiconductors.

Cyanated pentacenes are very promising candidate materials for ambipolar and n-type transistors. However, only a few examples have been obtained to date - all requiring lengthy, multi-step processes. Herein, we present the first preparation of 5,7,12,14-tetracyanopentacene (TCP) and a facile, scaled-up preparation of 6,13-dicyanopentacene (DCP). Both compounds are prepared by a one-pot synthesis using cheap quinones as starting materials. Detailed crystallographic investigations evince that the bulk assemblies of both cyanated pentacenes are dominated by non-covalent interactions, resulting in a dense, stable, face-to-face packing and in an intriguing packing motif for TCP. Very low frontier molecular orbital energy levels and a reversible bleaching of TCP are revealed by cyclic voltammetry. Finally, both cyanated pentacenes are used in proof-of-concept organic thin-film transistors (OTFTs) operating under ambient conditions. This work highlights the potential of cyanation for larger acenes and presents a straightforward route to the rational design of this promising class of materials.

Geomimetics and Extreme Biomimetics Inspired by Hydrothermal Systems-What Can We Learn from Nature for Materials Synthesis?

'Extreme biomimetics' and 'geomimetics' are relatively recent fields of materials chemistry. Both take inspiration from natural materials for generating novel synthetic materials or enhanced properties in known materials. In geomimetics, the source of inspiration is geological systems, while extreme biomimetics is motivated by organisms operating in-from an anthropocentric point of view-extreme conditions. This review article focuses on geomimetic and extreme biomimetic hydrothermal synthesis. Since hydrothermal preparative chemistry typically uses nothing but water and the required precursors, the field belongs to the research area of 'green materials chemistry'. Geomimetics, on the one hand, takes inspiration from natural materials formation. Extreme Biomimetics, on the other hand, is inspired by materials found in extremophile organisms, instead of aiming to implement their actual biosynthesis. In this contribution, both extreme biomimetics and geomimetics are first defined, and further critically discussed on the basis of recent, selected examples. Moreover, the necessity for the two closely related fields as well their prospects are commented on.

Extending the Scope of a New Cyanation: Design and Synthesis of an Anthracene Derivative with an Exceptionally Low LUMO Level and Improved Solubility.

The preparation of cyanated acenes from quinones has been improved for the conversion of electron-poor starting materials. The new procedure was used to prepare rationally designed 2,7-dinitro-9,10-dicyanoanthracene. Crystallographic, morphological, and electrochemical investigations have revealed most promising properties for applications in organic electronics.