Structure, Dynamics, and Reactivity of Encapsulated Molecules in Restricted Spaces: Arylazoisoxazoles within an Octa Acid Capsule.

In this study, a well-defined organic capsule assembled from two octa acid (OA) molecules acting as host and select arylazoisoxazoles (AAIO) acting as guests were employed to demonstrate that confined molecules have restricted freedom that translates into reaction selectivity in both ground and excited states. The behavior of these AAIO guests in confined capsules was found to be different from that found in both crystals, where there is very little freedom, and in isotropic solvents, where there is complete freedom. Through one-dimensional (1D) and two-dimensional (2D) 1H NMR spectroscopic experiments, we have established a relationship between structure, dynamics and reactivity of molecules confined in an OA capsule. Introduction of CF3 and CH3 substitution at the 4-position of the aryl group of AAIO reveals that in addition to space confinement, weak interactions between the guest and the OA capsule control the dynamics and reactivity of guest molecules. 1H NMR studies revealed that there is a temperature-dependence to guest molecules tumbling (180° rotation along the capsular short axis) within an OA capsule. While 1H NMR points to the occurrence of tumbling motion, MD simulations and simulation of the temperature-dependent NMR signals provide an insight into the mechanism of tumbling within OA capsules. Thermal and photochemical isomerization of AAIO were found to occur within an OA capsule just as in organic solvents. The observed selectivity noted during thermal and photo induced isomerization of OA encapsulated AAIOs can be qualitatively understood in terms of the well-known concepts due to Bell-Evans-Polanyi (BEP principle), Hammond and Zimmerman.

Environmental Markers of Plastics and Microplastics.

The slow reaction rates to chemical and photochemical degradation are well-known properties of plastics. However, large plastic surfaces exposed to environmental conditions release particles and compounds that affect ecosystems and human health. The aim of this work was to identify compounds associated with the degradation of polyethylene (PE), polystyrene (PS), and polyvinyl chloride (PVC) microplastics (markers) on silica and sand and evaluate their use to screen microplastics on natural sand. Products were identified by using targeted and untargeted LC-HRMS analysis. All polymers underwent chemical oxidation on silica. PE released dicarboxylic acids (HO2C-(CH2)n-CO2H (n = 4-30), while PS released cis/trans-chalcone, trans-dypnone, 3-phenylpropiophenone, and dibenzoylmethane. PVC released dicarboxylic acids and aromatic compounds. Upon irradiation, PE was stable while PS released the same compounds as under chemical oxidation but at lower yields. Under the above condition, PVC generated HO2C-[CH2-CHCl]n-CH2-CO2H and HO2C-[CH2-CHCl]n-CO2H (n = 2-19) dicarboxylic acids. The same products were detected on sand but at a lower concentration than on silica due to better retention within the pores. Detection of markers of PE and PS on natural sand allowed us to screen microplastics by following a targeted analysis. Markers of PVC were not detected before or after thermal/photo-oxidation due to the low release of compounds and limitations associated with surface exposure/penetration of radiation.

Ultrafast Processes in Upper Excited Singlet States of Free and Caged 7-Diethylaminothiocoumarin.

The photochemistry and photophysics of thiocarbonyl compounds, analogues of carbonyl compounds with sulfur, have long been overshadowed by their counterparts. However, recent interest in visible light reactions has reignited attention toward these compounds due to their unique excited-state properties. This study delves into the ultrafast dynamics of 7-diethylaminothiocoumarin (TC1), a close analogue of the well-known probe molecule coumarin 1 (C1), to estimate intersystem crossing rates, understand the mechanisms of fluorescence and phosphorescence, and evaluate TC1's potential as a solvation dynamics probe. Enclosing TC1 within an organic capsule indicates its potential applications, even in aqueous environments. Ultrafast studies reveal a dominant subpicosecond intersystem crossing process, indicating the importance of upper excited singlet and triplet states in the molecule's photochemistry. The distinct fluorescence and phosphorescence origins, along with the presence of closely spaced singlet excited states, support the observed efficient intersystem crossing. The sulfur atom alters the excited-state behavior, shedding light on reactive triplet states and paving the way for further investigations.

Application of molecular dynamic simulations in modeling the excited state behavior of confined molecules.

Relative to isotropic organic solvent medium, the structure and conformation of a reactant molecule in an organized and confining medium are often different. In addition, because of the rigidity of the immediate environment, the reacting molecule have a little freedom to undergo large changes even upon gaining energy or modifications in the electronic structure. These alterations give rise to differences in the photochemistry of a molecular and supramolecular species. In this study, one such example is presented. α-Alkyl dibenzylketones upon excitation in isotropic solvents give products via Norrish type I and type II reactions that are independent of the chain length of the alkyl substituent. On the other hand, when these molecules are enclosed within an organic capsule of volume ~ 550 Å3, they give products that are strikingly dependent on the length of the α-alkyl substitution. These previously reported experimental observations are rationalized based on the structures generated by molecular modeling (docking and molecular dynamics (MD) simulations). It is shown that MD simulations that are utilized extensively in biologically important macromolecules can also be useful to understand the excited state behavior of reactive molecules that are part of supramolecular assemblies. These simulations can provide structural information of the reactant molecule and the surroundings complementing that with the one obtained from 1 and 2D NMR experiments. MD simulated structures of seven α-alkyl dibenzylketones encapsulated within the octa acid capsule provide a clear understanding of their unique behavior in this restricted medium. Because of the rigidity of the medium, these structures although generated in the ground state can rationalize the photochemical behavior of the molecules in the excited state.

Spectroscopic Insights of an Emissive Complex between 4'-N,N-Diethylaminoflavonol in Octa-Acid Deep-Cavity Cavitand and Rhodamine 6G.

Excited-state chemistry relies on the communication between molecules, making it a crucial aspect of the field. One important question that arises is whether intermolecular communication and its rate can be modified when a molecule is confined. To explore the interaction in such systems, we investigated the ground and excited states of 4'-N,N-diethylaminoflavonol (DEA3HF) in an octa acid-based (OA) confined medium and in ethanolic solution, both in the presence of Rhodamine 6G (R6G). Despite the observed spectral overlap between the flavonol emission and the R6G absorption, as well as the fluorescence quenching of the flavonol in the presence of R6G, the almost constant fluorescence lifetime at different amounts of R6G discards the presence of FRET in the studied systems. Steady-state and time-resolved fluorescence indicate the formation of an emissive complex between the proton transfer dye encapsulated within water-soluble supramolecular host octa acid (DEA3HF@(OA)2) and R6G. A similar result was observed between DEA3HF:R6G in ethanolic solution. The respective Stern-Volmer plots corroborate with these observations, suggesting a static quenching mechanism for both systems.

Keeping the name clean: [2 + 2] photocycloaddition.

Crossed [2 + 2] photocycloaddition is a specific case of intramolecular photocycloaddition reaction. Recently, the term "crossed [2 + 2] photocycloaddition" is interchangeably used to represent intermolecular [2 + 2] photocycloaddition reactions of two dissimilar double bonds/alkenes. To avoid confusion and to help researchers use the correct terminologies, this perspective clarifies the terminology used for different [2 + 2] photocycloaddition processes based on prior literature with the hope of establishing a standard for addressing the diverse set of photocycloaddition reactions that will be helpful to the chemical community.

Ultrafast Excited State Dynamics of Spatially Confined Organic Molecules.

This Feature 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 S2. 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.

Vibration-Assisted Intersystem Crossing in the Ultrafast Excited-State Relaxation Dynamics of Halocoumarins.

Due to its numerous applications, triplet formation and resulting phosphorescence remain a frontier area of research for over eight decades. Facile intersystem crossing (ISC) is the primary requirement for triplet formation and observation of phosphorescence. The incorporation of a heavy atom in molecules is one of the common approaches employed to facilitate ISC. A detailed study of the excited state dynamics that governs ISC is necessary to understand the mechanism of heavy atom effect (HAE). Incorporation of iodine at the 3 position of coumarin-1 reduces fluorescence quantum yield (ϕf) drastically as expected, whereas bromine substitution at the same position increased the ϕf. Such a contrasting effect of the two heavy atoms suggests that there are other features yet to be discovered to fully understand the HAE. Detailed steady state and femtosecond transient absorption studies along with theoretical calculations suggest that the C3-X (X = Br, I) bond vibration plays an important role in the ISC process. The study reveals that while in the case of the iodo-derivative there is no energy barrier in the singlet triplet crossing path, there is a barrier in the case of the bromo-derivative, which slows the ISC process. Such an unexpected phenomenon is not limited to halocoumarins as this rationalizes the photobehavior of 1-bromo-/iodo-substituted naphthalenes as well.

Modulation of Reduction Potentials of Bis(pyridinium)alkane Dications through Encapsulation within Cucurbit[7]uril.

Supramolecular modulation of reduction potentials of two series of bis(pyridinium)alkane salts is described. Study of the encapsulation of bis(pyridinium)alkane guests within the CB[7] cavity revealed the critical influence of the linker length and the position of the heteroatom on the reduction potentials of encapsulated guests. CB[7] complexation of pyridinium salts induced reduction potential changes ranging between +50 and -430 mV. Noncovalent modulation of the electron-accepting ability of organic cations can be utilized in electron-transfer-initiated reactions.

Visible-Light-Triggered Selective Intermolecular [2+2] Cycloaddition of Extended Enones: 2-Oxo-3-enoates and 2,4-Dien-1-ones with Olefins.

Photosensitization has recently re-emerged owing to the current interest in visible-light catalysis. One of the photoreactions investigated in this context, namely, photo[2+2]cycloaddition of olefins, is established to show high selectivity and wide generality. Here, we describe the results of our studies on selective intermolecular cycloaddition between extended enones (2,4-dien-1-ones and 2-oxo-3-enoates) and olefins under visible-light sensitization. With Ru(bpy)3Cl2 as the triplet energy sensitizer, [2+2] addition of 2,4-dien-1-ones to olefins resulted in the addition to the "ene" part of enones with high efficiency. Generality and functional group tolerance were established by examining a number of enones. 2-Oxo-3-enoates also underwent addition to olefins in the presence of Ru(phen)3(PF6)2. Both additions were more efficient in the presence of the triplet sensitizer than upon direct irradiation. No Paternò-Büchi product was detected. Density functional theory calculations revealed the origin of high selectivity in the two extended enone systems. Together with spectroscopic studies and control experiments, the cycloaddition has been demonstrated to occur from the excited triplet state of these extended enones, which were generated via the energy transfer process.

Ultrafast Solvation Dynamics Reveal that Octa Acid Capsule's Interior Dryness Depends on the Guest.

Coumarins are well-known to exhibit environment-dependent excited-state behavior. We have exploited this feature to probe the accessibility of solvent water molecules to coumarins (guest) encapsulated within an organic capsule (host). Two sets of coumarins, one small that fits well within the capsule and the other larger that fits within an enlarged capsule, are used as guests. In our study, the two sets of coumarins serve different purposes: one is employed to explore electron transfer across the capsule and the other to release photoprotected acids into the aqueous environment. The capsule is made up of two molecules of octa acid (OA) and is soluble in an aqueous medium under slightly basic conditions. Molecular modeling studies revealed that while the OA capsule is fully closed with no access to water in the case of smaller coumarins, with the larger molecules, the capsule is not tight and the guest is in contact with water molecules, the number being dependent on the size of the coumarin. We have used the ultrafast time-dependent Stokes shift method to understand the solvent dynamics around the above guest molecules encapsulated within an OA capsule in an aqueous medium. Results depict that for the smaller sets of coumarins, water cannot access the guests within the OA cavity during their excited state lifetime. However, the case is completely different for the larger coumaryl esters. Distorted capsule structure exposes the guest to water, and a dynamics Stokes shift is observed. The average solvation time decreases with the increasing size of guests that clearly indicates accessibility of the encapsulated guests toward greater number of water molecules as the capsule structure distorts with increasing size of the guests. Results of the ultrafast solvation dynamics are consistent with that of molecular dynamics simulation.

Ultrafast trans → cis Photoisomerization Dynamics of Alkyl-Substituted Stilbenes in a Supramolecular Capsule.

Ultrafast spectroscopy reveals the effects of confinement on the excited-state photoisomerization dynamics for a series of alkyl-substituted trans-stilbenes encapsulated in the hydrophobic cavity of an aqueous supramolecular organic host-guest complex. Compared with the solvated compounds, encapsulated trans-stilbenes have broader excited-state absorption spectra, excited-state lifetimes that are 3-4 times longer, and photoisomerization quantum yields that are 1.7-6.5 times lower in the restricted environment. The organic capsule disrupts the equilibrium structure and restricts torsional rotation around the central C═C double bond in the excited state, which is an important motion for the relaxation of trans-stilbene from S1 to S0. The location and identity of alkyl substituents play a significant role in determining the excited-state dynamics and photoisomerization quantum yields by tuning the relative crowding inside the capsule. The results are discussed in terms of distortions of the ground- and excited-state potential energy surfaces, including the topology of the S1-S0 conical intersection.

Achiral Zeolites as Reaction Media for Chiral Photochemistry.

Obtaining enantiomerically-enriched photoproducts from achiral reactants has been a long-sought goal. The various methods developed to achieve chiral induction in photoproducts during the last fifty years still suffer from a lack of predictability, generality, and simplicity. With the current emphasis on green chemistry, obtaining enantiomerically enriched products via photochemistry is a likely viable alternative for the future. Of the various approaches developed during the last three decades, the one pioneered in the author's laboratory involved the use of commercially-available and inexpensive achiral zeolites as the media. This approach does not use any solvent for the reaction. Examples from these studies are highlighted in this article. Since no chiral zeolites were available, when the work was initiated in the author's laboratory, commercially-available zeolites X and Y were modified with chiral inductors so that the reaction space becomes chiral. The results obtained established the value of chirally-modified, commercial zeolites as media for achieving chiral induction in photochemical reactions. A recent report of the synthesis of a chiral zeolite is likely to stimulate zeolite-based chiral photochemistry in synthesizing enantiomerically-pure organic molecules. The availability of chiral zeolites in future is likely to energize research in this area. Our earlier observations on this topic, we believe, would be valuable for progress of the field. Keeping this in mind, I have summarized the work carried out in our laboratory on chiral photochemistry on chirally-modified zeolites. This review does not include examples where high chiral induction has been obtained via a strategy that examines molecules appended with chiral auxiliary within achiral and chirally-modified zeolites. The latter approach yields products with diastereomeric excess >80%.

Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition.

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.

Photocatalysis with Quantum Dots and Visible Light: Selective and Efficient Oxidation of Alcohols to Carbonyl Compounds through a Radical Relay Process in Water.

Selective oxidation of alcohols to aldehydes/ketones has been achieved with the help of 3-mercaptopropionic acid (MPA)-capped CdSe quantum dot (MPA-CdSe QD) and visible light. Visible-light-prompted electron-transfer reaction initiates the oxidation. The thiyl radical generated from the thiolate anion adsorbed on a CdSe QD plays a key role by abstracting the hydrogen atom from the C-H bond of the alcohol (R1 CH(OH)R2 ). The reaction shows high efficiency, good functional group tolerance, and high site-selectivity in polyhydroxy compounds. The generality and selectivity reported here offer a new opportunity for further applications of QDs in organic transformations.

General and Efficient Intermolecular [2+2] Photodimerization of Chalcones and Cinnamic Acid Derivatives in Solution through Visible-Light Catalysis.

[2+2] Photocycloaddition, for example, the dimerization of chalcones and cinnamic acid derivatives, is a unique strategy to construct cyclobutanes, which are building blocks for a variety of biologically active molecules and natural products. However, most attempts at the above [2+2] addition have focused on solid-state, molten-state, or host-guest systems under ultraviolet-light irradiation in order to overcome the competition of facile geometric isomerization of nonrigid olefins. We report a general and simple method to realize the intermolecular [2+2] dimerization reaction of these acyclic olefins to construct cyclobutanes in a highly regio- and diastereoselective manner in solution under visible light, which provides an efficient solution to a long-standing problem.

Photochemistry within a water-soluble organic capsule.

Photochemistry along with life as we know it originated on earth billions of years ago. Supramolecular Photochemistry had its beginning when plants that sustain life began transforming water into oxygen by carrying out light initiated reactions within highly organized assemblies. Prompted by the efforts of J. Priestly (photosynthesis), F. Sestini, S. Cannizaro, and C. Liebermann (solid-state photochemistry of santonin, quinones, and cinnamic acid), orderly scientific investigations of the link between light absorption by matter and molecules and the chemical and physical consequences began in the mid-1700s. By 1970 when Molecular Photochemistry had matured, it was clear that controlling photochemical reactions by conventional methods of varying reaction parameters like temperature and pressure would be futile due to the photoreactions' very low activation energies and enthalpies. During the last 50 years, the excited state behavior of molecules has been successfully manipulated with the use of confining media and weak interactions between the medium and the reactant molecule. In this context, with our knowledge from experimentation with micelles, cyclodextrins (CD), cucurbitruils (CB), calixarenes (CA), Pd nanocage, crystals, and zeolites as media, we began about a decade ago to explore the use of a new water-soluble synthetic organic cavitand, octa acid (OA) as a reaction container. The uniqueness of OA as an organic cavitand lies in that two OA molecules form a closed hydrophobic capsule to encapsulate water-insoluble guest molecule(s). The ability to include a large number of guest molecules in OA has provided an opportunity to examine the excited state chemistry of organic molecules in a hydrophobic, confined environment. OA distinguishes itself from the well-known cavitands CD and CB by its active reaction cavity absorbing UV-radiation between 200 and 300 nm and serving as energy, electron, and hydrogen donor. The freedom of guest molecules in OA, between that in crystals and isotropic solution can be transformed into photoproducts selectivity. The results of our photochemical investigations elaborated in this Account demonstrate that OA with a medium sized cavity exerts better control on excited state processes than the more common and familiar organic hosts such as CD, CB, CA, and micelles. By examining the photochemistry of a number of molecules (olefins, carbonyls, aromatics and singlet oxygen) that undergo varied reactions (cleavage, cycloaddition, cis-trans isomerization, oxidation and cyclization) within OA capsule, we have demonstrated that the free space within the container, the capsule influenced conformation and preorientation of guest molecules, supramolecular steric control, and capsular dynamics contribute to the altered excited state behavior. In this Account, we have shown that photochemistry based on concepts of physical organic and supramolecular chemistry continues to be a discipline with unlimited potential. The future of supramolecular photochemistry lies in synthetic, materials, medicinal, and biological chemistries. Success in these areas depends on synthesizing well-designed water-soluble hosts that can emulate complex biological assemblies, organizing and examining the behavior of supramolecular assemblies on solid surfaces, rendering the photoreactions catalytic, and delivering encapsulated drugs in a targeted fashion.

A Phosphorescent Platinum(II) Bipyridyl Supramolecular Polymer Based on Quadruple Hydrogen Bonds.

A platinum(II) bipyridyl complex bearing bis-ureidopyrimidinone (Pt-bisUPy) has been designed and its self-assembling behavior has been thoroughly investigated by 1 H NMR, DOSY NMR, Ubbelohde viscometry analysis, UV/Vis, and emission spectroscopies. Pt-bisUPy underwent concentration-dependent ring-chain polymerization in apolar solvents. Hydrogen-bonding interactions play an important role during the formation of the supramolecular polymers. Hydrogen-bonded supramolecular polymers were transformed to nanoparticles in water through the miniemulsion method. These nanoparticles showed strong π-π excimeric emission. Metal-metal-to-ligand charge transfer (MMLCT) from Pt-Pt interactions was not significant in the emission spectrum. The phosphorescence of the nanoparticle persisted even under aerobic conditions. The triplet state of these phosphorescent nanomaterials were long-lived and possessed moderate emission quantum yields. Furthermore, the low toxicity of these materials promises a place for them in in vitro and in vivo bioimaging.

Room temperature phosphorescence from a guest molecule confined in the restrictive space of an organic-inorganic supramolecular assembly.

Stable room-temperature phosphorescence of guest aromatic molecules was achieved by the effective suppression of oxygen quenching. The organic capsule (first wall) suppressed static oxygen quenching by enclosing a guest molecule, and dynamic quenching via the capsule opening-closing process was well suppressed and manipulated by the intercalation of this capsule into the restrictive space between clay nanosheets (second wall).

Sequential energy and electron transfer in a three-component system aligned on a clay nanosheet.

To achieve the goal of energy transfer and subsequent electron transfer across three molecules, a phenomenon often utilized in artificial light harvesting systems, we have assembled a light absorber (that also serves as an energy donor), an energy acceptor (that also serves as an electron donor) and an electron acceptor on the surface of an anionic clay nanosheet. Since neutral organic molecules have no tendency to adsorb onto the anionic surface of clay, a positively charged water-soluble organic capsule was used to hold neutral light absorbers on the above surface. A three-component assembly was prepared by the co-adsorption of a cationic bipyridinium derivative, cationic zinc porphyrin and cationic octaamine encapsulated 2-acetylanthracene on an exfoliated anionic clay surface in water. Energy and electron transfer phenomena were monitored by steady state fluorescence and picosecond time resolved fluorescence decay. The excitation of 2-acetylanthracene in the three-component system resulted in energy transfer from 2-acetylanthracene to zinc porphyrin with 71% efficiency. Very little loss due to electron transfer from 2-acetylanthracene in the cavitand to the bipyridinium derivative was noticed. Energy transfer was followed by electron transfer from the zinc porphyrin to the cationic bipyridinium derivative with 81% efficiency. Analyses of fluorescence decay profiles confirmed the occurrence of energy transfer and subsequent electron transfer. Merging the concepts of supramolecular chemistry and surface chemistry we realized sequential energy and electron transfer between three hydrophobic molecules in water. Exfoliated transparent saponite clay served as a matrix to align the three photoactive molecules at a close distance in aqueous solutions.