Addressing Charge-Transfer and Locally-Excited States in a Twisted Biphenyl Push-Pull Chromophore.

We present the synthesis and spectroscopic characterization of a twisted push-pull biphenyl molecule undergoing photoinduced electron transfer. Steady-state and transient absorption spectra suggest, in this rigid molecular structure, a subtle interplay between locally-excited and charge-transfer states, whose equilibrium and dynamics is only driven by solvation. A theoretical model is presented for the solvation dynamics and, with the support of quantum chemical calculations, we demonstrate the existence of two sets of states, having either local or charge-transfer character, that only "communicate" thanks to solvation, which is the sole driving force for the charge-separation process.

CO2-induced single-crystal to single-crystal transformations of an interpenetrated flexible MOF explained by in situ crystallographic analysis and molecular modeling.

A molecular-level investigation is reported on breathing behaviour of a metal-organic framework (1) in response to CO2 gas pressure. High-pressure gas adsorption shows a pronounced step corresponding to a gate-opening phase transformation from a closed (1cp ) to a large-pore (1lp ) form. A plateau is observed upon desorption corresponding to narrow-pore intermediate form 1np which does not occur during adsorption. These events are corroborated by pressure-gradient differential scanning calorimetry and in situ single-crystal X-ray diffraction analysis under controlled CO2 gas pressure. Complete crystallographic characterisation facilitated a rationalisation of each phase transformation in the series 1cp → 1lp → 1np → 1cp during adsorption and subsequent desorption. Metropolis grand-canonical Monte Carlo simulations and DFT-PBE-D3 interaction energy calculations strongly underpin this first detailed structural investigation of an intermediate phase encountered upon desorption.

Superlinear amplification of the first hyperpolarizability of linear aggregates of DANS molecules.

A bottom-up modelling strategy is adopted to discuss the linear and nonlinear optical spectra of a prototypical push-pull dye, 4-dimethylamino-4'-nitrostilbene (DANS), in different environments, from solutions to linear aggregates, fully accounting for the molecular polarity and polarizability. In particular, we demonstrate a large amplification of the first hyperpolarizability of linear aggregates with a superlinear dependence on the aggregate size. Results are discussed with reference to recent experiments for DANS molecules aligned inside single-wall carbon nanotubes, leading to a complete and internally consistent description of the observed spectral properties in terms of ∼7 aligned molecules, reducing by an order of magnitude the size of the aggregate estimated in the hypothesis of linear amplification, as expected for non-interacting molecules. This has important implications for material design: it is possible to obtain a large amplification of the first hyperpolarizability by aligning just a few DANS molecules (or more generally, a few polar dyes showing normal solvatochromism) without the need to grow large ordered systems.

Functional corannulene: diverse structures, enhanced charge transport, and tunable optoelectronic properties.

Chemical functionalization of various hydrocarbons, such as coronene, corannulene, and so forth, shows good promise in electronics applications because of their tunable optoelectronic properties. By using quantum chemical calculations, we have investigated the changes in the corannulene buckybowl structure, which greatly affect its electronic and optical properties when functionalized with different electron-withdrawing imide groups. We find that the chemical nature and position of functional groups strongly regulate the stacking geometry, π-stacking interactions, and electronic structure. Herein, a range of optoelectronic properties and structure-property relationships of various imide-functionalized corannulenes are explored and rationalized in detail. In terms of carrier mobility, we find that the functionalization strongly affects the reorganization energy of corannulene, while the enhanced stacking improves hopping integrals, favoring the carrier mobility of crystals of pentafluorophenylcorannulene-5-monoimide. The study shows a host of emerging optoelectronic properties and enhancements in the charge-transport characteristics of functionalized corannulene, which may find possible semiconductor and electronics applications.