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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. 

Combining hyperspectral and polarimetric imaging provides a powerful sensing modality with broad applications from astronomy to biology. Existing methods rely on temporal data acquisition or snapshot imaging of spatially separated detectors. These approaches incur fundamental artifacts that degrade imaging performance. To overcome these limitations, we present a stomatopod-inspired sensor capable of snapshot hyperspectral and polarization sensing in a single pixel. The design consists of stacking polarization-sensitive organic photovoltaics (P-OPVs) and polymer retarders. Multiple spectral and polarization channels are obtained by exploiting the P-OPVs’ anisotropic response and the retarders’ dispersion. We show that the design can sense 15 spectral channels over a 350-nanometer bandwidth. A detector is also experimentally demonstrated, which simultaneously registers four spectral channels and three polarization channels. The sensor showcases the myriad degrees of freedom offered by organic semiconductors that are not available in inorganics and heralds a fundamentally unexplored route for simultaneous spectral and polarimetric imaging. 

Polarimeters have broad applications in remote sensing, astronomy, and biomedical imaging to measure the emitted, reflected, or transmitted state of polarization. An intrinsic coincident (IC) full-Stokes polarimeter was previously demonstrated by our group, in a free space configuration, by using stain-aligned polymer-based organic photovoltaics. To minimize the model’s complexity, these were tilted to avoid crosstalk from back-reflections. We present a theoretical model of a monolithic IC polarimeter that considers the back-reflection’s influence for on-axis light. The model was validated using a monolithic four-detector polarimeter, which achieved an error of less than 3%. Additionally, an off-axis model was produced and validated for a simpler two detector polarimeter, demonstrating an error between the TM and TE polarized components of less than 3% for angles spanning an 18° incidence cone.