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The unique environment within the core of carbaporphyrinoid systems provides a platform to explore unusual organometallic chemistry. The ability of these structures to form stable organometallic derivatives was first demonstrated for N-confused porphyrins but many other carbaporphyrin-type systems were subsequently shown to exhibit similar or complementary properties. Metalation commonly occurs with catalytically active transition metal cations and the resulting derivatives exhibit widely different physical, chemical and spectroscopic properties and range from strongly aromatic to nonaromatic and antiaromatic species. Metalation may trigger unusual, highly selective, oxidation reactions. Alkyl group migration has been observed within the cavity of metalated carbaporphyrins, and in some cases ring contraction of the carbocyclic subunit takes place. Over the past thirty years, studies in this area have led to multiple synthetic routes to carbaporphyrinoid ligands and remarkable organometallic chemistry has been reported. An overview of this important area is presented.
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Diamond Chemistry: Advances and Perspectives
Abstract Diamond as a material has many unique properties. Its high optical dispersion, extraordinarily high mechanical strength, and unparalleled thermal conductivity have long made it a material of interest for applications such as high‐temperature electronics and as wear‐resistance coatings. More recently, diamond has emerged as a material with a wide range of applications in chemistry and biology. The high intrinsic stability of diamond, coupled with the ability to modify diamond surfaces with a wide range of inorganic, organic, and biological species via highly stable covalent linkages, provides a wealth of opportunity to couple diamond's chemical properties with its extraordinary physical properties. The practical utility of diamond has been greatly expanded in recent years through dramatic advances in the ability to produce diamond in bulk, thin film, and nanoparticle form, with controlled doping and purity at modest cost. These advances, together with diamond's highly stable and tunable surface chemistry with versatility of physical structure enable a wide range of emerging applications of interest to chemists, including quantum science, biomedicine, energy storage, and catalysis. Yet, to fully exploit the unique properties of diamond, some formidable chemical challenges lie ahead. We begin by reviewing some of the features of diamond that are of particular importance to the chemistry community. We aim to highlight some of the important applications where diamond chemistry plays a key role, identify some of the key observations, and outline some of the future directions and opportunities for diamond in the chemical world.
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- Award ID(s):
- 2001611
- PAR ID:
- 10636298
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 64
- Issue:
- 25
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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