A fundamental aim in the field of catalysis is the development of new modes of small molecule activation. One approach toward the catalytic activation of organic molecules that has received much attention recently is visible light photoredox catalysis. In a general sense, this approach relies on the ability of metal complexes and organic dyes to engage in single-electron-transfer (SET) processes with organic substrates upon photoexcitation with visible light.

Many of the most commonly employed visible light photocatalysts are polypyridyl complexes of ruthenium and iridium, and are typified by the complex tris(2,2′-bipyridine) ruthenium(II), or Ru(bpy)32+ (Figure 1). These complexes absorb light in the visible region of the electromagnetic spectrum to give stable, long-lived photoexcited states.1,2 The lifetime of the excited species is sufficiently long (1100 ns for Ru(bpy)32+) that it may engage in bimolecular electron-transfer reactions in competition with deactivation pathways.3 Although these species are poor single-electron oxidants and reductants in the ground state, excitation of an electron affords excited states that are very potent single-electron-transfer reagents. Importantly, the conversion of these bench stable, benign catalysts to redox-active species upon irradiation with simple household lightbulbs represents a remarkably chemoselective trigger to induce unique and valuable catalytic processes.






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Figure 1


Ruthenium polypyridyl complexes: versatile visible light photocatalysts.

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Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis

As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

Photoinduced reactivity of titanium dioxide

In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.

Organic Photoredox Catalysis

The use of visible light sensitization as a means to initiate organic reactions is attractive due to the lack of visible light absorbance by organic compounds, reducing side reactions often associated with photochemical reactions conducted with high energy UV light. This tutorial review provides a historical overview of visible light photoredox catalysis in organic synthesis along with recent examples which underscore its vast potential to initiate organic transformations.

Visible light photoredox catalysis: applications in organic synthesis

Photocatalysis (by semiconductors, molecules and ions) is used in such diverse applications as water hydrolysis for producing hydrogen as fuel, organic synthesis and the recovery of polluted effluents. This tutorial review discusses the common principles of such applications and their role in green chemistry.

Photocatalysis. A multi-faceted concept for green chemistry

Photocatalysis for the formation of the C-C bond.

Inorganic and organic UV filters: Their role and efficacy in sunscreens and suncare products

Acylation of electrophilic olefins through decatungstate-photocatalyzed activation of aldehydes.

In the context of seed technology, the use of physical methods for increasing plant production offers advantages over conventional treatments based on chemical substances. The effects of physical invigoration treatments in seeds can be now addressed at multiple levels, ranging from morpho-structural aspects to changes in gene expression and protein or metabolite accumulation. Among the physical methods available, "magneto-priming" and irradiation with microwaves (MWs) or ionizing radiations (IRs) are the most promising pre-sowing seed treatments. "Magneto-priming" is based on the application of magnetic fields and described as an eco-friendly, cheap, non-invasive technique with proved beneficial effects on seed germination, vigor and crop yield. IRs, as γ-rays and X-rays, have been widely regarded as a powerful tool in agricultural sciences and food technology. Gamma-rays delivered at low dose have showed to enhance germination percentage and seedling establishment, acting as an actual 'priming' treatment. Different biological effects have been observed in seeds subjected to MWs and X-rays but knowledge about their impact as seed invigoration agent or stimulatory effects on germination need to be further extended. Ultraviolet (UV) radiations, namely UV-A and UV-C have shown to stimulate positive impacts on seed health, germination, and seedling vigor. For all mentioned physical treatments, extensive fundamental and applied research is still needed to define the optimal dose, exposition time, genotype- and environment-dependent irradiation conditions. Electron paramagnetic resonance has an enormous potential in seed technology not fully explored to monitor seed invigoration treatments and/or identifying the best suitable irradiation dose or time-point to stop the treatment. The present manuscript describes the use of physical methods for seed invigoration, while providing a critical discussion on the constraints and advantages. The future perspectives related to the use of these approaches to address the need of seed technologists, producers and trade markers will be also highlighted.

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Daniele Dondi

Papers

Photocatalysis. A multi-faceted concept for green chemistry

Photocatalysis for the formation of the C-C bond.

Inorganic and organic UV filters: Their role and efficacy in sunscreens and suncare products

Acylation of electrophilic olefins through decatungstate-photocatalyzed activation of aldehydes.

Physical Methods for Seed Invigoration: Advantages and Challenges in Seed Technology.