A new class of push−pull dyes based on the reactive isobenzofuran core have been synthesized. The new dyes have a smaller HOMO−LUMO gap than a related class of dyes based on benzofurazan and allow for isolation of structural factors that contribute to environmental sensitivity. Experimental and theoretical evidence implicate different photophysical processes are responsible for a reversal of emissive behavior that is observed between isobenzofuran and benzofurazan analogues.
Self-assembled monolayers (SAMs) are predicated on thermodynamic equilibrium hence their properties project accessible relaxation pathways. Herein, we demonstrate that charge tunneling correlates with conformational degrees of freedom(s). Results from open and closed head-groups show that, as expected, distribution in tunneling data correlates with the orientation of the head-group, akin to the odd-even effect, and more importantly the degree of conformational freedom but fluctuates with applied bias. Trends in nature of distributions in current density illuminates the need for higher statistical moments in understanding these rather dynamic systems. We employ skewness, kurtosis and estimation plots to show that conformational degree of freedom in the head group significantly amplifies the odd-even effect and may lead to enhanced or perturbed tunneling based on whether the head group is on an odd-or even-parity spacer.
Differentiation of heterocyclic isomers
by solution 1H, 13C, and 15N NMR
spectroscopy is often challenging
due to similarities in their spectroscopic signatures. Here, 13C{14N} solid-state NMR spectroscopy experiments
are shown to operate as an “attached nitrogen test”,
where heterocyclic isomers are easy to distinguish based on one-dimensional
nitrogen-filtered 13C solid-state NMR. We anticipate that
these NMR experiments will facilitate the assignment of heterocyclic
isomers during synthesis and natural product discovery.
An unexpected nucleophilic aromatic substitution lead
to a novel
benzothiadiazole scaffold that bore the functional group pattern associated
with benzyl-type photocleavable protecting groups. The new molecules
display efficient photochemical release of leaving groups with blue
light. The performance of both ortho- and meta-substituted derivatives
was probed through both structural manipulation and computational
metrics to improve performance.
A strategy to control the efficiency of a photocleavage reaction based on changing the nature of the excited state is presented. A novel class of photoactive compounds has been synthesized by combining the classical o-nitrobenzyl scaffold with an environmentally sensitive dye, 4-aminonitrobenzothiazole. Irradiation in a polar solvent lead to an excited state that is inoperative for photochemistry whereas excitation in a nonpolar solvent lead to an excited state that is photochemically active. A photochemical degradation appears to be the preferred process in contrast to the intended photocleavage process.
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