RESUMO
The potential for realizing robust, monolithic, near-surface refractive micro-optic elements with long-lived stability is demonstrated in visible and infrared transmitting glasses capable of use in dual band applications. Employing an enhanced understanding of glass chemistry and geometric control of mobile ion migration made possible with electrode patterning, flat, permanent, thermally-poled micro-optic structures have been produced and characterized. Sub-surface (t~5-10 µm) compositional and structural modification during the poling process results in formation of spatially-varying refractive index profiles, exhibiting induced Δn changes up to 5 × 10-2 which remain stable for >15 months. The universality of this approach applied to monolithic vis-near infrared [NIR] oxide and NIR-midwave infrared [MIR] chalcogenide glass materials is demonstrated for the first time. Element size, shape and gradient profile variation possible through pattern design and fabrication is shown to enable a variety of design options not possible using other GRIN process methodologies.
RESUMO
A combined experimental-theoretical investigation has revealed that oxazine-based compounds are multiaddressable, multistate, and multifunctional molecular switches exhibiting contrasts of both linear and second-order nonlinear optical properties. The switching properties are particularly large when the substituent is a donor group. In this study, the cleavage of the C-O bond at the junction of the indole and oxazine cycles (of the closed a forms) is acido-triggered, leading to an open form (b(+)) characterized by larger first hyperpolarizabilities (ßHRS) and smaller excitation energies than in the closed form. These results are confirmed and interpreted utilizing ab initio calculations that have been carried out on a broad set of compounds to unravel the role of the substituent. With respect to acceptor groups, oxazines bearing donor groups are characterized not only by larger ßHRS and ßHRS contrast ratios but also by smaller excitation energies, larger opening-induced charge transfer, and reduction of the bond length alternation, as well as smaller Gibbs energies of the opening reaction. Compared to protonated open forms (b(+)), calculations on the zwitterionic open forms (b) have pointed out similarities in the long-wavelength UV/vis absorption spectra, whereas their ßHRS values might differ strongly as a function of the substituent. Indeed, the open forms present two NLOphores, the indoleninium-substituent entity and the nitrophenol (present in the protonated open form, b(+)) or nitrophenolate (present in the zwitterionic open form, b) moiety. Then, nitrophenolate displays a larger first hyperpolarizability than nitrophenol and the ß tensor of the two entities might reinforce or cancel each other.
RESUMO
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.
RESUMO
In this work, linear and nonlinear optical properties of electro-/acido-/photoswitchable indolino[2,1-b]oxazolidine derivatives were investigated. The linear optical properties of the closed and open forms have been characterized by UV-visible and IR spectroscopies associated with DFT calculations. Nonlinear optical properties of the compounds have been obtained by ex situ and in situ hyper-Rayleigh experiments in solution. We show that protonated, oxidized, and irradiated open forms exhibit the same visible absorption and NLO features. In particular, the closed and open forms exhibit a huge contrast of the first hyperpolarizability with an enhancement factor of 40-45. Additionally, we have designed an original electrochemical cell that allows to monitor in situ the hyper-Rayleigh response upon electrical stimulus. We report notably a partial but good and reversible NLO contrast in situ during oxidation/reduction cycles. Thereby, indolinooxazolidine moieties are versatile trimodal switchable units which are very promising for applications in devices.
