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.

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.

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.

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.

Functionalized mesoporous solids based on magadiite and [Al]-magadiite.

Novel hybrid mesoporous and functionalized materials with controllable surface area and pore dimensions with functional basic sites (-NH2) were synthesized from magadiite and [Al]-magadiite as layered silicate precursors. The variable pore structure and properties of these materials were investigated in these solids by using different CTA(+)/Na(+) (CTA(+) = cetyltrimethylammonium cation) molar ratios in the pre-modification step with aminopropyltriethoxysilane (APTS) and tetraethoxysilane (TEOS). Characterizations were carried out by different techniques to probe the effects of the amounts of interlayer surfactant in the synthesis of the pillared and/or grafted materials. The crystalline structures of magadiite and [Al]-magadiite layers were maintained as evidenced by FT-IR and SAED and contain pillars and aminopropyl groups in the interlayer space. The hybrid solids were compared to the pillared forms (H. M. Moura, F. A. Bonk and H. O. Pastore, Eur. J. Mineral., 2012, 24, 903) and to the aminopropyl-grafted forms and presented the properties of both solids with the CO2 adsorption capability improved considerably.