Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds

Organic materials that exhibit thermally activated delayed fluorescence (TADF) are an attractive class of functional materials that have witnessed a booming development in recent years. Since Adachi et al. reported high-performance TADF-OLED devices in 2012, there have been many reports regarding the design and synthesis of new TADF luminogens, which have various molecular structures and are used for different applications. In this review, we summarize and discuss the latest progress concerning this rapidly developing research field, in which the majority of the reported TADF systems are discussed, along with their derived structure–property relationships, TADF mechanisms and applications. We hope that such a review provides a clear outlook of these novel functional materials for a broad range of scientists within different disciplinary areas and attracts more researchers to devote themselves to this interesting research field.

Recent advances in organic thermally activated delayed fluorescence materials.

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C–H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C–H activation until summer 2018.

3d Transition Metals for C-H Activation.

Organic reactions that involve the direct functionalization of non-activated C–H bonds represent an attractive class of transformations which maximize atom- and step-economy, and simplify chemical synthesis. Due to the high stability of C–H bonds, these processes, however, have most often required harsh reaction conditions, which has drastically limited their use as tools for the synthesis of complex organic molecules. Following the increased understanding of mechanistic aspects of C–H activation gained over recent years, great strides have been taken to design and develop new protocols that proceed efficiently under mild conditions and duly benefit from improved functional group tolerance and selectivity. In this review, we present the current state of the art in this field and detail C–H activation transformations reported since 2011 that proceed either at or below ambient temperature, in the absence of strongly acidic or basic additives or without strong oxidants. Furthermore, by identifying and discussing the major strategies that have led to these improvements, we hope that this review will serve as a useful conceptual overview and inspire the next generation of mild C–H transformations.

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Mild metal-catalyzed C–H activation: examples and concepts

Iron Catalysis in Organic Synthesis

Transient Directing Groups for Transformative C–H Activation by Synergistic Metal Catalysis

Two benzoylpyridine-carbazole based fluorescence materials DCBPy and DTCBPy, bearing two carbazolyl and 4-(t-butyl)carbazolyl groups, respectively, at the meta and ortho carbons of the benzoyl ring, were synthesized. These molecules show very small ΔEST of 0.03 and 0.04 eV and transient PL characteristics indicating that they are thermally activated delayed fluorescence (TADF) materials. In addition, they show extremely different photoluminescent quantum yields in solution and in the solid state: in cyclohexane the value are 14 and 36%, but in the thin films, the value increase to 88.0 and 91.4%, respectively. The OLEDs using DCBPy and DTCBPy as dopants emit blue and green light with EQEs of 24.0 and 27.2%, respectively, and with low efficiency roll-off at practical brightness level. The crystal structure of DTCBPy reveals a substantial interaction between the ortho donor (carbazolyl) and acceptor (4-pyridylcarbonyl) unit. This interaction between donor and acceptor substituents likely play a key role to ...

A New Molecular Design Based on Thermally Activated Delayed Fluorescence for Highly Efficient Organic Light Emitting Diodes

The transition metal-catalyzed transformation of otherwise inert C–H bonds into substituted alkenes offers a versatile tool for the synthesis of value added olefinic molecules. Recent developments in the directing group assisted C–H activation approach ensured high levels of positional selectivity. A vast number of coordinating groups have been utilized in directed C–H alkenylation, which are often not removable after the desired transformation. However, the concept of easily removable or traceless directing group strategy overcomes this limitation and enables site-selective C–H alkenylation of relevance to academia and the practitioners in industry. Various easily removable or transformable directing groups utilized in the transition metal-catalyzed oxidative C–H alkenylations are discussed in this review until February 2017.

Recent advances in positional-selective alkenylations: removable guidance for twofold C–H activation

ConspectusOver the last three decades, transition-metal-catalyzed organic transformations have been shown to be extremely important in organic synthesis. However, most of the successful reactions are associated with noble metals, which are generally toxic, expensive, and less abundant. Therefore, we have focused on catalysis using the abundant first-row transition metals, specifically cobalt. In this Account, we demonstrate the potential of cobalt catalysis in organic synthesis as revealed by our research.We have developed many useful catalytic systems using cobalt complexes. Overall, they can be classified into several broad types of reactions, specifically [2 + 2 + 2] and [2 + 2] cycloadditions; enyne reductive coupling; reductive [3 + 2] cycloaddition of alkynes/allenes with enones; reductive coupling of alkyl iodides with alkenes; addition of organoboronic acids to alkynes, alkenes, or aldehydes; carbocyclization of o-iodoaryl ketones/aldehydes with alkynes/electron-deficient alkenes; coupling of thio...

Parthasarathy Gandeepan

Papers

3d Transition Metals for C-H Activation.

Transient Directing Groups for Transformative C–H Activation by Synergistic Metal Catalysis

A New Molecular Design Based on Thermally Activated Delayed Fluorescence for Highly Efficient Organic Light Emitting Diodes

Recent advances in positional-selective alkenylations: removable guidance for twofold C–H activation

Cobalt Catalysis Involving π Components in Organic Synthesis