Switches that can be actively steered
by external stimuli along
multiple pathways at the molecular level are the basis for next-generation
responsive material systems. The operation of commonly employed molecular
photoswitches revolves around one key structural coordinate. Photoswitches
with functionalities that depend on and can be addressed along multiple
coordinates would offer novel means to tailor and control their behavior
and performance. The recently developed donor–acceptor Stenhouse
adducts (DASAs) are versatile switches suitable for such applications.
Their photochemistry is well understood, but is only responsible for
part of their overall photoswitching mechanism. The remaining thermal
switching pathways are to date unknown. Here, rapid-scan infrared
absorption spectroscopy is used to obtain transient fingerprints of
reactions occurring on the ground state potential energy surface after
reaching structures generated through light absorption. The spectroscopic
data are interpreted in terms of structural transformations using
kinetic modeling and quantum chemical calculations. Through this combined
experimental–theoretical approach, we are able to unravel the
complexity of the multidimensional ground-state potential energy surface
explored by the photoswitch and use this knowledge to predict, and
subsequently confirm, how DASA switches can be guided along this potential
energy surface. These results break new ground for developing user-geared
DASA switches but also shed light on the development of novel photoswitches
in general.
Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O-O and O-N, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner-contrary to textbook knowledge. This explains experimentally observed qualitative differences between O-O and O-N collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.
The molecular structure around metal ions in polymer materials has puzzled researchers for decades. This question has acquired new relevance with the discovery that aged oil paint binders can adopt an ionomer structure when metal ions leached from pigments bind to carboxylate groups on the polymerized oil network. The characteristics of the metal-polymer structure are expected to have important consequences for the rate of oil paint degradation reactions such as metal soap formation and oil hydrolysis. Here, we use two-dimensional infrared (2D-IR) spectroscopy to demonstrate that zinc carboxylates formed in paint films containing zinc white pigment adopt either a coordination chain– or an oxo-type cluster structure. Moreover, it was found that the presence of water governs the relative concentration of these two types of zinc carboxylate coordination. The results pave the way for a molecular approach to paintings conservation and the application of 2D-IR spectroscopy to the study of polymer structure.
Genetic fitting algorithm accounting for the uncertainty in computed energies allows a significantly more reliable assignment of stereochemistry and conformational heterogeneity of chiral compounds using vibrational circular dichroism.
Upon cooling in solution, chiral triarylamine tris‐amide unimers produce organogels by stacking into helical supramolecular polymers, which subsequently bundle into larger fibers. Interestingly, circular dichroism, vibrational circular dichroism, and AFM imaging of the chiral self‐assemblies revealed that monocolumnar P‐helical fibrils formed upon fast cooling, whereas bundled M‐superhelical fibers formed upon slow cooling. The mechanistic study of this structural bifurcation reveals the presence of a strong memory effect, reminiscent of a complex stepwise combination of primary and secondary nucleation‐growth processes. These results highlight the instrumental role of sequential self‐assembly processes to control supramolecular architectures of multiple hierarchical order.
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