An intrinsically stretchable and bendable electrochromic device.

Stretchable electrochromic devices (ECDs) were fabricated from electrospun PEDOT:PSS (poly(3, 4-ethylenedioxythiophene):polystyrene sulfonate) fibers. Stretchable and transparent electrodes with a sheet resistance of 1200 Ω sq-1were prepared by depositing the conductive fibers on elastomeric substrates that were prepared from polydimethylsiloxane. The conductive substrates replaced the ITO coated glass electrodes that are typically used in ECDs. The functioning device was prepared from a flexible chitosan electrolytic gel and a 4, 7-bis(4-diphenylaminophenyl)-2, 1, 3-benzothiaziazole (TPA-BZT-TPA) electrochrome that were deposited on the streatchable transparent electrodes. The assembled device could be stretched to 150% its original length and bent to a curvature of 0.1. The device could be operated and switched between its yellow (off) and blue (on) states while being stretched and bent with a maximum contrast ΔT ≈ 30% at 805 nm and a coloration efficiency of 168 cm2C-1. The stretchable device had an electrochromic contrast that was 30% greater than its counterpart that was prepared from conventional ITO-glass electrodes. The critical composition required for making devices truly stretchable was possible by evaluating the performance of five types of devices consisting of different layers.

Dynamics of Anthracene Excimer Formation within a Water-Soluble Nanocavity at Room Temperature.

Excited anthracene is well-known to photodimerize and not to exhibit excimer emission in isotropic organic solvents. Anthracene (AN) forms two types of supramolecular host-guest complexes (2:1 and 2:2, H:G) with the synthetic host octa acid in aqueous medium. Excitation of the 2:2 complex results in intense excimer emission, as reported previously, while the 2:1 complex, as expected, yields only monomer emission. This study includes confirming of host-guest complexation by NMR, probing the host-guest structure by molecular dynamics simulation, following the dynamics AN molecules in the excited state by ultrafast time-resolved experiments, and mapping of the excited surface through quantum chemical calculations (QM/MM-TDDFT method). Importantly, time-resolved emission experiments revealed the excimer emission maximum to be time dependent. This observation is unique and is not in line with the textbook examples of time-independent monomer-excimer emission maxima of aromatics in solution. The presence of at least one intermediate between the monomer and the excimer is inferred from time-resolved area normalized emission spectra. Potential energy curves calculated for the ground and excited states of two adjacent anthracene molecules via the QM/MM-TDDFT method support the model proposed on the basis of time-resolved experiments. The results presented here on the excited-state behavior of a well-investigated aromatic molecule, namely the parent anthracene, establish that the behavior of a molecule drastically changes under confinement. The results presented here have implications on the behavior of molecules in biological systems.

Remote electron and energy transfer sensitized photoisomerization of encapsulated stilbenes.

Excited state chemistry and physics of molecules, in addition to their inherent electronic and steric features, depend on their immediate microenvironments. This study explores the influence of an organic capsule, slightly larger than the reactant molecule itself, on the excited state chemistry of the encapsulated molecule. Results presented here show that the confined molecule, in fact, is not isolated and can be manipulated from outside even without direct physical interaction. Examples where communication between a confined molecule and a free molecule present outside is brought about through electronic and energy transfer processes are presented. Geometric isomerization of octa acid encapsulated stilbenes induced by energy and electron transfer by cationic sensitizers that attach themselves to the anionic capsule is examined. The fact that isomerization occurs when the sensitizer present outside is excited illustrates that the reactant and sensitizer are communicating across the molecular wall of the capsule. Ability to remotely activate a confined molecule opens up new opportunities to bring about reactions of confined radical ions and triplet excited molecules generated via long distance energy and electron transfer processes.

Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes.

Ultrafast transient absorption spectroscopy reveals new excited-state dynamics following excitation of trans-azobenzene (t-Az) and several alkyl-substituted t-Az derivatives encapsulated in a water-soluble supramolecular host-guest complex. Encapsulation increases the excited-state lifetimes and alters the yields of the trans → cis photoisomerization reaction compared with solution. Kinetic modeling of the transient spectra for unsubstituted t-Az following nπ* and ππ* excitation reveals steric trapping of excited-state species, as well as an adiabatic excited-state trans → cis isomerization pathway for confined molecules that is not observed in solution. Analysis of the transient spectra following ππ* excitation for a series of 4-alkyl and 4,4'-dialkyl substituted t-Az molecules suggests that additional crowding due to lengthening of the alkyl tails results in deeper trapping of the excited-state species, including distorted trans and cis structures. The variation of the dynamics due to crowding in the confined environment provides new evidence to explain the violation of Kasha's rule for nπ* and ππ* excitation of azobenzenes based on competition between in-plane inversion and out-of-plane rotation channels.

Reversal of Regioselectivity during Photodimerization of 2-Anthracenecarboxylic Acid in a Water-Soluble Organic Cavitand.

The value of octa acid (OA) as a reaction vessel in steering a photoreaction toward a less favored product was established. Photodimerization of 2-anthracenecarboxylic acid within OA yields exclusively head-to-head dimers, while in media such as solution, cyclodextrins (CD) and related hosts yield predominantly head-to-tail dimers. Further, OA enhances the chiral selectivity on the product dimers. The difference between OA and CD is attributed to the variation in the dimensions of their entry ports.

Supramolecular photochemistry of encapsulated caged ortho-nitrobenzyl triggers.

ortho-Nitrobenzyl (oNB) triggers have been extensively used to release various molecules of interest. However, the toxicity and reactivity of the spent chromophore, o-nitrosobenzaldehyde, remains an unaddressed difficulty. In this study we have applied the well-established supramolecular photochemical concepts to retain the spent trigger o-nitrosobenzaldehyde within the organic capsule after release of water-soluble acids and alcohols. The sequestering power of organic capsules for spent chromophores during photorelease from ortho-nitrobenzyl esters, ethers and alcohols is demonstrated with several examples.

Space Constrained Stereoselective Geometric Isomerization of 1,2-Diphenylcyclopropane and Stilbenes in an Aqueous Medium.

Confinement provided by the reaction space alters the photostationary state isomer distribution during the geometric isomerization of excited 1,2-diphenylcyclopropane and stilbenes. The selectivity in 1,2-diphenylcyclopropane is suggested to result from the supramolecular steric hindrance exerted by the medium for the rotational motion. The alteration in the selectivity between a dimethyl and n-propyl substituted stilbenes is attributed to the medium influence on the location of the transition state on the ground state surface.