Structural Aspects and Templation of Photochemistry in Solid‐State Supramolecular Systems

Kaftory, Menahem

doi:10.1002/9781118095300.ch7

Cited by 6 publications

(3 citation statements)

References 97 publications

(51 reference statements)

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“…Toda and co-workers using diacetylene diols listed in Scheme that formed a cage-like structure in the solid state preorganized a number of olefins toward dimerization. − These hosts formed inclusion complexes with olefins only in the solid state. In these inclusion complexes the reactive olefins are isolated within a small space and brought within 4.2 Å.…”

Section: Organic Crystals As a Supramolecular Assemblymentioning

confidence: 99%

“…It is important to note that benzylideneacetophenone alone crystallized in two polymorphic modifications with the center-to-center distance between the double bonds of 5.2 and 4.8 Å. Dibenzylideneacetone yielded the all-trans dimer in solution and was light stable in the solid state. The diacetylene diol host DH-1 templates not only [2 + 2] dimerization but also [4 + 4] dimerization of a few systems as well. ,, …”

Section: Organic Crystals As a Supramolecular Assemblymentioning

confidence: 99%

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Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition

2016

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Photochemistry, bearing significant applications in natural and man-made events such as photosynthesis, vision, photolithography, photodynamic therapy, etc., is yet to become a common tool during the synthesis of small molecules in a laboratory. Among other rationale, the inability to influence photochemical reactions with temperature, solvent, additives, etc., dissuades chemists from employing light-initiated reactions as a routine synthetic tool. This review highlights how diverse, highly organized structures such as solvent-free crystals and water-soluble host-guest assemblies can be employed to control and manipulate photoreactions and thereby serve as an efficient tool for chemists, including those interested in synthesis. The efficacy of the media in modifying the excited-state behavior of organic molecules is illustrated with photocycloaddition in general and [2 + 2] photocycloaddition in particular, reactions widely employed in the synthesis of complex natural products as well as highly constrained molecules, as exemplars. The reaction media, highly pertinent in the context of green sustainable chemistry, include solvent-free crystals and solids such as silica, clay, and zeolite and water-soluble hosts that can solubilize and preorganize hydrophobic reactants in water. Since no other reagent would be more sustainable than light and no other medium greener than water, we believe that the supramolecular photochemistry expounded here has a momentous role as a synthetic tool in the future.

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Section: Organic Crystals As a Supramolecular Assemblymentioning

confidence: 99%

Section: Organic Crystals As a Supramolecular Assemblymentioning

confidence: 99%

Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition

2016

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“…The dimer is formed through a [4 + 4] cycloaddition, which involves a pair of carbon–carbon double bonds on two distinct molecules lying adjacent in the crystal lattice. For a long time, it has been recognized − that the dimerization mechanism proceeds via the formation of an excimer intermediate, or physical dimer, obtained by electronic excitation of the monomer. In agreement with the topochemical postulate, the course of the reaction is determined by parameters depending on the monomer crystal packing, such as distances between the potentially reactive atoms of the two adjacent molecules, relative orientations of the anthracene skeletons and lateral shifts between the orbitals of the reactive atoms .…”

Section: Introductionmentioning

confidence: 99%

Micro Raman Investigation of the Photodimerization Reaction of 9-Cyanoanthracene in the Solid State

et al. 2014

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The classic photodimerization reaction of 9-cyanoanthracene in the solid state has been studied by means of Raman microscopy, analyzing the time evolution both of the molecular and of the lattice phonon spectra from the reactant to the product. This has allowed us to verify that the formation of the dimer crystal structure always takes place with some delay with respect to the onset of the chemical reaction, as already observed in another crystal to crystal photoreaction. 1 This evidence points to a phenomenon of reconstructive phase transition. 2 The kinetic analysis of the spectroscopic data confirms the previous hypothesis of an autocatalytic mechanism for the process.

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Manipulating Intermediates The Photochemical Way

2013

Photochemically‐Generated Intermediates in Synthesis

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Structural Aspects and Templation of Photochemistry in Solid‐State Supramolecular Systems

Cited by 6 publications

References 97 publications

Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition

Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition

Micro Raman Investigation of the Photodimerization Reaction of 9-Cyanoanthracene in the Solid State

Manipulating Intermediates The Photochemical Way

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