Molecular solar thermal systems - control of light harvesting and energy storage by protonation/deprotonation

Molecular solar thermal (MOST) systems that undergo photoisomerizations to long-lived, high-energy forms present one approach of addressing the challenge of solar energy storage. For this approach to mature, photochromic molecules which can absorb at the right wavelengths and which can store a sufficient amount of energy in a controlled time period have to be developed. Here we show in a combined experimental and theoretical study that incorporation of a pyridyl substituent onto the dihydroazulene/vinylheptafulvene photo-/thermoswitch results in molecules whose optical properties, energy-releasing back-reactions and energy densities can be controlled by protonation/deprotonation. The work thus presents a proof-of-concept for using acid/base to control the properties of MOST systems

Tracking molecular resonance forms of donor-acceptor push-pull molecules by single-molecule conductance experiments

The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor–acceptor molecules. Here we report that donor–acceptor-substituted molecular wires also exhibit distinct properties in single-molecule electronics under the influence of a bias voltage, but in absence of solvent. Two oligo(phenyleneethynylene) wires with donor–acceptor substitution on the central ring (cruciform-like) exhibit remarkably broad conductance peaks measured by the mechanically controlled break-junction technique with gold contacts, in contrast to the sharp peak of simpler molecules. From a theoretical analysis, we explain this by different degrees of charge delocalization and hence cross-conjugation at the central ring. Thus, small variations in the local environment promote the quinoid resonance form (off), the linearly conjugated (on) or any form in between. This shows how the conductance of donor–acceptor cruciforms is tuned by small changes in the environment