The construction of molecular photogears that can achieve through-space transmission of the unidirectional double-bond rotary motion of light-driven molecular motors onto a remote single-bond axis is a formidable challenge in the field of artificial molecular machines. Here, we present a proof-of-principle design of such photogears that is based on the possibility of using stereogenic substituents to control both the relative stabilities of two helical forms of the photogear and the double-bond photoisomerization reaction that connects them. The potential of the design was verified by quantum-chemical modeling through which photogearing was found to be a favorable process compared to free-standing single-bond rotation ("slippage"). Overall, our study unveils a surprisingly simple approach to realizing unidirectional photogearing. A stereochemical approach to transmitting the directional double-bond rotary motion of light-driven molecular motors through space onto a remote single-bond axis is put forth and successfully tested by means of quantum-chemical modeling. A key result in the assessment of the approach is that the desired photogearing process is favorable compared to the undesired, free-standing single-bond rotation process ("slippage") with which it competes.**image

Photochemical reactions enabling efficient transformation of aromatic systems into energetic but stable non-aromatic isomers have a long history in organic chemistry. One recently discovered reaction in this realm is that where derivatives of 1,2-azaborine, a compound isoelectronic with benzene in which two adjacent C atoms are replaced by B and N atoms, form the non-hexagon Dewar isomer. Here, we report quantum-chemical calculations that explain both why 1,2-azaborine is intrinsically more reactive toward Dewar formation than benzene, and how suitable substitutions at the B and N atoms are able to increase the corresponding quantum yield. We find that Dewar formation from 1,2-azaborine is favored by a pronounced driving force that benzene lacks, and that a large improvement in quantum yield arises when the reaction of substituted 1,2-azaborines proceeds without involvement of an intermediary ground-state species. Overall, we report new insights into making photochemical use of the Dewar isomers of aromatic compounds. Quantum-chemical calculations combined with molecular-dynamics simulations reveal mechanisms for improving the quantum yields by which aromatic compounds form their non-aromatic Dewar isomers, with potential implications in solar-energy storage.

This work investigates the photophysics of barbituric acid at different pH conditions using ab initio methods. Our calculations ascribe the most intense bands at ca. 260 nm at neutral pH and 210 nm at acidic pH conditions in the absorption spectra of this chromophore to the lowest lying pi pi* transitions. Consistently with the ultrashort excited state lifetimes experimentally registered, the potential energy landscapes of both the neutral and deprotonated forms of barbituric acid combined with the interpretation of their transient absorption spectra suggest the deactivation of these systems along the singlet manifold. Compared to uracil, its closest natural nucleobase, barbituric acid presents a red shifted absorption spectrum, due to the lowering by more than 0.5 eV of the lowest-energy pi pi* excited state, and a much more complex topography of the S-1 potential energy surface, with several energetically accessible local minima. This fact, however, does not affect the excited state lifetimes, which for barbituric acid were experimentally registered in the sub-ps time scale.

The common approach to investigate the impact of aromaticity on excited-state proton transfer by probing the (anti)aromatic character of reactants and products alone is scrutinized by modelling such reactions involving 2-pyridone. Thereby, it is found that energy barriers can be strongly influenced by transient changes in aromaticity unaccounted for by this approach, particularly when the photoexcited state interacts with a second excited state. Overall, the modelling identifies a pronounced effect overlooked by most studies on this topic.