Combining Benzazolo-Oxazolidine Twins toward Multi-state Nonlinear Optical Switches.

Molecular switches are chemical compounds exhibiting the possibility of reversible transformations between their different forms accompanied by a modification in their properties. Among these, switching of multi-addressable Benzazolo-OXazolidines (BOXs) from a closed form to an open form results in drastic modifications in their linear and nonlinear optical properties. Here, we target molecules containing two identical BOX units (DiBOX) connected by different π-conjugated linkers, and we combine synthesis, UV/visible absorption, and hyper-Rayleigh scattering (HRS) measurements, together with density functional theory (DFT) calculations. Three derivatives have been considered, which differ by the linker: (i) a bithiophene moiety (Bt), (ii) two 3,4-ethylenedioxythiopene (EDOT) units, and (iii) a triad composed of an EDOT-thiophene-EDOT sequence (TtO). As a matter of fact, these systems can adopt three states (CF-CF, POF-POF, and CF-POF) depending on the closed form (CF) or the protonated open form (POF) of each BOX unit. Despite chemical equivalence, stepwise switching of such systems under the addition of a chemical acid or an oxidant has been experimentally evidenced for two of them (DiBOX-Bt and DiBOX-TtO). Then, DFT calculations show that the first BOX opening leads to the formation of a push-pull π-conjugated segment, exhibiting a huge increase in the first hyperpolarizability (ß) and a bathochromic shift with respect to the fully closed form. On the contrary, the second BOX opening induces not only a slight bathochromic shift but also a reduction in their ß values conferring the great and uncommon abilities to modulate their linear and nonlinear properties over three discrete levels. Among these results, those on DiBOX-Bt agree with the experimental data obtained by HRS measurements and further shed light on their structure-property relationship.

Unraveling the Effects of Co-Crystallization on the UV/Vis Absorption Spectra of an N-Salicylideneaniline Derivative. A Computational RI-CC2 Investigation.

This work aims at unraveling the effects of co-crystallization on the optical properties of an N-salicylideneaniline-derived molecular switch transforming between an enol and a keto form. This is achieved by way of a two-step multi-scale method where (i) the molecular geometry and unit cell parameters are optimized using a periodic boundary conditions density functional theory method and (ii) the optical properties are computed for a selection of clusters embedded in an array of point-charges that reproduce the crystal field electronic potential. The optical properties (vertical excitation energies and oscillator strengths) are obtained at the RI-CC2/def2-TZVPD level of approximation. This method allows us to decompose the effects of co-crystallization into (i) indirect effects, the geometry changes of the chromophore due to crystal packing with the coformer, and (ii) direct ones, the polarization due to the interacting coformer and to the crystal field. For the former effects, variations of a crucial torsion angle lead to modification of the π-conjugation and therefore to the decrease or increase of the excitation energies. About the latter, they are antagonistic: (i) the coformer is not directly involved in the excitations but its polarization decreases the excitation energies while (ii) the crystal field has the opposite effect. For the co-crystals with succinic and fumaric acids, combining these direct and indirect effects leads to a hypsochromic shift of the first absorption band with respect to the reference crystal, in agreement with experimental data.

Periodic DFT Study of the Effects of Co-Crystallization on a N-Salicylideneaniline Molecular Switch.

This work aims at better understanding the complex effects of co-crystallization on a single salicylideneaniline molecular switch, (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3), which can tautomerize between an enol and a keto form. A combination of periodic boundary conditions DFT and molecular wavefunction calculations has been adopted for examining a selection of PYV3 co-crystals, presenting hydrogen bonds (H-bonds) or halogen bonds (X-bonds), for which X-ray diffraction data are available. Three aspects are targeted: i) the energy (H-bond strength, enol to keto relative energy, and geometry relaxation energies), ii) the geometrical structure (PYV3 to co-crystal and enol to keto geometrical variations), and iii) the electron distribution (PYV3 to co-crystal and enol to keto Mulliken charge variations). These allow i) explaining the preference for forming H-bonds with the nitrogen of the pyridine of PYV3 with respect to the oxygens and the importance of the crystal field, ii) distinguishing the peculiar behavior of the SulfonylDiPhenol (SDP) coformer, which stabilizes the keto form of PYV3, iii) describing the relative stabilization of the enol form upon co-crystallization (with the exception of SDP) and therefore iv) substantiating the co-crystallization-induced reduction of thermochromism observed for several PYV3 co-crystals.

Second-Order Nonlinear Optical Properties of a Dithienylethene-Indolinooxazolidine Hybrid: A Joint Experimental and Theoretical Investigation.

The nonlinear optical (NLO) properties of a double photochrome molecular switch are reported for the first time by considering the four trans forms of a dithienylethene-indolinooxazolidine hybrid. The four forms are characterized by means of hyper-Rayleigh scattering (HRS) experiments and quantum chemical calculations. Experimental measurements provide evidence that the pH- and light-triggered transformations between the different forms of the hybrid are accompanied by large variations of the first hyperpolarizability, which makes this compound an effective multistate NLO switch. Quantum chemical calculations conducted at the time-dependent Hartree-Fock and time-dependent DFT levels agree with the experimental data and allow a complete rationalization of the NLO responses of the different forms. The HRS signal of the forms with an open indolinooxazolidine moiety are more than one order of magnitude larger than that measured for the other forms, whereas the open/closed status of the dithienylethene subunit barely influences the dynamic NLO properties. However, extrapolation of the NLO responses to the static limit leads to univocally distinguishable intrinsic responses for three of the various forms. This hybrid system thus acts as a highly efficient multistate NLO switch for eventual exploitation in optical memory systems with multiple storage and nondestructive readout capacity.

Explicit versus implicit solvation effects on the first hyperpolarizability of an organic biphotochrome.

The first hyperpolarizability of the four trans forms of a dithienylethene indolinooxazolidine biphotochrome in acetonitrile solution has been evaluated by using two solvation models, an explicit and an implicit one. The implicit solvation model is the integral equation formalism of the polarizable continuum model (IEF-PCM), whereas in the explicit one, the solvent molecules are represented by point charges, of which the positions have been generated by Monte Carlo simulations whereas the solute is treated quantum mechanically. At optical frequencies, first hyperpolarizabilities calculated with the implicit solvation model are usually larger than those obtained with the multiscale approach. However, both approaches predict similar contrasts, indicating that implicit solvation models such as IEF-PCM are well-suited to describe the variations in the NLO responses of molecular switches. In addition, the analysis of the contrasts of first hyperpolarizabilities shows that the biphotochrome can act as a three-state NLO switch.