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Photoreactive guests

In this review, only results relative to co-crystalline materials exhibiting fluorescent guests, photoreactive guests (possibly suitable for optical memories), and polar guest (possibly suitable for nonlinear optics and ferroelectric-ity) will be briefly reviewed. [Pg.210]

It is not easy to control the steric course of photoreactions in solution. Since molelcules are ordered regularly in a crystal, it is rather easy to control the reaction by carrying out the photoreaction in a crystal. However, molecules are not always arranged at an appropriate position for efficient and stereoselective reaction in their crystals. In these cases inclusion chemistry is a useful technique, as it can be employed to position molecules appropriately in the host-guest structure. Chiral host compounds are especially useful in placing prochiral and achiral molecules in suitable positions to yield the desired product upon photoirradiation. Some controls of the steric course of intramolecular and intermolelcular photoreactions in inclusion complexes with a host compound are described. [Pg.32]

Control and Acceleration of Photoreactions via Host-Guest Complex Formation... [Pg.218]

Control and Acceleration of Photoreactions via Host-Guest Complex Formation by a Solid-Solid Reaction and Irradiation in the Solid State... [Pg.231]

An enantioselective photoreaction of a guest compound is expected when an inclusion complex of the guest with an optically active host compound is irradiated in the solid state. [Pg.234]

The exploitation of the reactivity of molecular crystals lies close to the origins of crystal engineering and is at the heart of the pioneering work of Schmidt [47a]. The idea is that of organizing molecules in the solid state using the principles of molecular recognition and self-assembly. Successful results have been obtained with bimolecular reactions, particularly [2+2] photoreactivity and cyclisation [47b,c]. Another important area is that of host-guest chemistry. [Pg.29]

Surfaces. Preference in orientation of the substrates on the surfaces of silica, due to cavity wall-guest interactions, may also lead to some regio- and stereoselectivity. Examples of photoreactions of steriodal enones provided by de Mayo and co-workers illustrate the principles involved [173-175]. In these examples, the surface serves as a template when guest molecules are adsorbed on it. [Pg.137]

Solid inclusion complexes of photoreactive ketones with cyclodextrins as hosts (Figure 6) provide interesting examples of how a fairly stiff, somewhat heterogeneous (in terms of polarity, size, and guest orientation) reaction... [Pg.200]

Use of chiral single crystals to convert achiral reactants to chiral products in high optical yield application to die di-Jt-methane and Norrish type II photorearrangements, J. Am. Chem. Soc., 108, 5648-5649. (b) Chen, J., Pokkuluri, P. R., Scheffer, J. R., and Trotter J. (1990) Absolute asymmetric induction differences in dual pathway photoreactions, Tetrahedron Lett., 31, 6803-6806. (c) Fu, T. Y., Liu, Z., Scheffer, J. R., and Trotter, J. (1993) Supramolecular photochemistry of crystalline host-guest assemblies absolute asymmetric photorearrangement of the host component, J. Am. Chem. Soc., 115, 12202-12203. (d) Leibovitch, M.,... [Pg.131]

The example of vision demonstrates the profound influence of a protein matrix on the photochemistry of its constituent cofactor (guest molecule). This occurs by stabilization of unstable conformers and strained geometries and by fixation of the relative arrangements of systems of co-factors and generation of contacts between co-factors. Although the complexity of the structure of the protein precludes their use in everyday laboratory control of photoreactions, the lessons learned from the example of vision (and photosynthesis) are useful in designing media that provide better control of photoreactions than that obtained in isotropic solution. Let us compare the site (termed the reaction cavity) at which the reaction occurs in a protein and an isotropic solution medium. [Pg.557]

Situation (I) corresponds to a fluid isotropic solution where a uniform time averaged environment should exist. Under such conditions single exponential decay would be expected for the guest excited states and the photoreactivity should be predictable on the basis of a single effective reaction cavity. In situation (II) there should be two kinetically distinct excited states in two noninterconverting sites resulting in nonexponential decay of the excited state of A. The quantum efficiency of product formation and the product distribution may depend upon the percent conversion. An example of mechanism (II) is provided in Sch. 22 [137]. The ratio of products A, B, and C has been shown to depend on the crystal size. With the size of the crystal the ratio of molecules present on the surface and in the interior changes which results in different extents of reactions from two the distinct sites namely, surface and interior. [Pg.586]

The observed photobehavior of the benzaldehyde-CDx complexes in the solid state is unique and completely different from that of these complexes in aqueous solution and also from that of benzaldehyde 36 in organic solvents. The substantial formation of 4-benzoylbenzaldehyde 38 upon irradiation in (3- and y-CDx cavities indicates that these medium-sized CDx s provide the radical pair within a fairly spacious supercage environment, thus allowing the para-rearrangement (Scheme 13). The formation of practically racemic 37 upon irradiation of the y-CDx complex may also be attributed to the looser orientation of benzaldehyde 36 in the y-CDx cavity than in the (3-CDx cavity. It was thus demonstrated that the chiral hydrophobic cavity of native cyclodextrins not only modifies the photoreactivity of the included guest but also functions as a chiral supramolecular environment for photochirogenesis, albeit resulting in only modest ee%. [Pg.359]

CDx and in particular 7-CDx are known to accommodate two aromatic moieties under certain circumstances. Hence if two appropriate prochiral guest molecules are included in the same CDx cavity, regio- and enantioselective bimolecular photoreactions are expected to occur [108]. Indeed, it is known that the presence of CDx not only accelerates the rate but also modifies the product distribution of photocyclodimerizations of anthracene derivatives [109-111], coumarin derivatives [113-115], stilbene derivatives [116,117], stilbazole [118], and tranilast [119]. For instance, Tamaki and coworkers reported significantly enhanced quantum yields of photodimerization of anthracenesulfonates and anthracenecarboxyl-ates in the presence of 3- and 7-CDx [109-111]. These anthracene derivatives form 2 2 and 2 1 guest-host complexes with (3- and 7-CDx, respectively, and... [Pg.362]

The host-guest and ionic chiral auxiliary approaches have been most intensively applied for solid-state asymmetric induction. A number of achiral organic compounds could be converted into chiral compounds in high enantioselectivities. However, all the photoreactions in themselves are well-known intramolecular photoreactions photocyclization, [2 + 2] photocyclization, Norrish type II photo-cyclization, di-ir-methane photorearrangement and photoisomerization. New types of asymmetric photoreactions have never been reported. [Pg.494]

The photoreaction investigated to test the above model is the well-known electron-transfer-initiated intermolecular hydrogen abstraction reaction of carbonyl compounds [277]. Under the conditions employed, one of the guest mole-... [Pg.575]


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See also in sourсe #XX -- [ Pg.211 ]




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