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The [2+2] photocycloaddition (PCA [2+2]) of alkenes is one of the most synthetically useful photoreactions. It is a convenient one‐step reaction that is useful for generating substituted cyclobutanes, polymers, and biologically relevant molecules. However, the reaction efficiency is limited by its bimolecular nature requiring encounter between two reactants within the narrow window of excited state lifetime of the photoactive alkene, and competition from the unimolecular photoisomerization. Our groups have utilized macrocyclic cavitands, especially cucurbiturils(CB), to confine two alkene molecules within their cavities and steer them towards a single dimer regio‐ and stereoselectively. Although, primarily the review focuses on photocycloaddition within CBs, such reactions in closely related cavitands such as cyclodextrins (CD) and calixarenes (CA) are also briefly mentioned to provide a comparison with CBs. Studies on photocycloaddition of olefins within CB by other research groups are also briefly highlighted. A mechanistic model, with ability to predict the nature of the dimer product formed within the above reaction containers is included.

 

This article highlights the role of spatial confinement in controlling the fundamental behavior of molecules. Select examples illustrate the value of using space as a tool to control and understand excited state dynamics through a combination of ultrafast spectroscopy and conventional steady state methods. Molecules of interest were confined within a closed molecular capsule, derived from a cavitand known as octa acid (OA), whose internal void space is sufficient to accommodate molecules as long as tetracene and as wide as pyrene. The free space, i.e. the space that is left following the occupation of the guest within the host, is shown to play a significant role in altering the behavior of guest molecules in the excited state. The results reported here suggest that in addition to weak interactions that are commonly emphasized in supramolecular chemistry, the extent of empty space (i.e. the remaining void space within the capsule) is important in controlling the excited state behavior of confined molecules on ultrafast time scales. For example, the role of free space in controlling the excited state dynamics of guest molecules is highlighted by probing the cis-trans isomerization of stilbenes and azobenzenes within the OA capsule. Isomerization of both types of molecule are slowed when they are confined within a small space, with encapsulated azobenzenes taking a different reaction pathway compared to that in solution upon excitation to S¬2. In addition to steric constraints, confinement of reactive molecules in a small space helps to override the need for diffusion to bring the reactants together, thus enabling the measurement of processes that occur faster than the time scale for diffusion. The advantages of reducing free space and confining reactive molecules are illustrated by recording unprecedented excimer emission from anthracene and by measuring ultrafast electron transfer rates across the organic molecular wall. By monitoring the translational motion of anthracene pairs in a restricted space it has been possible to document the pathway undertaken by excited anthracene from inception to the formation of the excimer on the excited state surface. Similarly, ultrafast electron transfer experiments pursued here have established that the process is not hindered by a molecular wall. Apparently, the electron can cross the OA capsule wall provided the donor and acceptor are in close proximity. Measurements on the ultrafast time scale provide crucial insights for each of the examples presented here, emphasizing the value of both ‘space’ and ‘time’ in controlling and understanding the dynamics of excited molecules. 

Exerting control on excited state processes has been a long-held goal in photochemistry. One approach to achieve control has been to mimic biological systems in Nature ( e.g. , photosynthesis) that has perfected it over millions of years by performing the reactions in highly organized assemblies such as membranes and proteins by restricting the freedom of reactants and directing them to pursue a select pathway. The duplication of this concept at a smaller scale in the laboratory involves the use of highly confined and organized assemblies as reaction containers. This article summarizes the studies in the author's laboratory using a synthetic, well-defined reaction container known as octa acid (OA). OA, unlike most commonly known cavitands, forms a capsule in water and remains closed during the lifetime of the excited states of included molecules. Thus, the described excited state chemistry occurs in a small space with hydrophobic characteristics. Examples where the photophysical and photochemical properties are dramatically altered, compared to that in organic solvents wherein the molecules are freely soluble, are presented to illustrate the value of a restricted environment in controlling the dynamics of molecules on an excited state surface. While the ground state complexation of the guest and host is controlled by well-known concepts of tight-fit, lock and key, complementarity, etc. , free space around the guest is necessary for it to be able to undergo structural transformations in the excited state, where the time is short. This article highlights the role of free space during the dynamics of molecules within a confined, inflexible reaction cavity. 

Low temperature matrix isolation method is the most popular one to generate and store reactive molecules and characterize them by in-situ IR spectroscopy. Recognizing the need for a simpler method to trap and store such molecules and characterize by NMR spectroscopy at room temperature in solution we have performed experiments exploring the value of water-soluble octa acid (OA) capsule as a storage vessel. The molecule we have chosen to illustrate the feasibility is the highly hindered 7-cis--ionone, which has been established to exist in equilibrium with its cyclic form with the later favored at room temperature. In this study we have shown that confined space can be an alternative to temperature to tilt an equilibrium towards higher energy isomer. During the course of the study, we were surprised to note that 7-trans--ionone aggregates in water and have distinct 1H NMR spectra. Ability to assemble characterizable organic aggregates in water reveals the value of water as a reaction medium that is yet to be fully explored by photochemists. Finally, we have clarified the likely mechanism of secondary photoreaction of -pyran to the final photoproduct that involves 1,5-hydrogen migration. 

Organic solvents have been the sought-after medium to achieve light initiated transformations in laboratories and industries. Given the current emphasis on green chemistry and rising awareness of environmental pollution it may be necessary for us to utilize abundantly freely available, non-toxic and environmentally friendly water as the medium to perform photoreactions. Although water has attracted the attention of organic synthetic chemists, it is yet to receive the indispensable attention of photochemists. In this article we present examples of photocycloaddition reactions of four molecules namely coumarin, indene, cinnamic acid and acenaphthylene that are sparingly soluble in water. Photodimerization of these molecules in water is much faster and occurs at much lower concentrations than in organic solvents. Aggregation probably forced by hydrophobic association is suggested to be the cause for the increased reactivity even at lower concentrations. The dimer distribution in water is different from that in organic solvents. Further work is required to fully understand the mechanism of photodimerization in water. Although the poor solubility of organic molecules in water requires one to irradiate large volumes to collect enough useful amounts, availability of flow reactors and LEDs as light sources should help one overcome the challenges.