RESUMO
Three series of push-pull derivatives bearing 4H-pyranylidene as electron donor group and a variety of acceptors were designed. On one hand, one-dimensional chromophores with a thiophene ring (series 1H) or 5-dimethylaminothiophene moiety (series 1N) as an auxiliary donor, non-coplanar with the π-conjugated system, were synthesized. On the other hand, related two-dimensional (2D) Y-shaped chromophores (series 2) were also prepared to compare how the diverse architectures affect the electrochemical, linear, and second-order nonlinear optical (NLO) properties. The presence of the 5-dimethylaminothiophene moiety in the exocyclic CâC bond of the pyranylidene unit gives rise to oxidation potentials rarely low, and the protonation (with an excess of trifluoroacetic acid) of its derivatives results in the apparition of a new blue-shifted band in the UV-visible spectra. The analysis of the properties of derivatives with and without the additional thiophene ring shows that this auxiliary donor leads to a higher NLO response, accompanied by an enhanced transparency. Y-shaped chromophores of series 2 present a blue-shifted absorption, higher molar extinction coefficients, and higher Eox values compared to their linear twisted counterparts. As concerns NLO properties, 2D Y-shaped architecture gives rise to somewhat lower µß values (except for thiobarbiturate derivatives).
RESUMO
The present work takes advantage of the self-assembly process occurring along organogelation, to organize Second Harmonic Generation (SHG) active chromophores. To do so, three push-pull chromophores endowed with a dodecyl urea chain were synthesized and characterized. Their organogelating properties were studied in a wide range of solvents. Despite similar architectures, these derivatives exhibit very different gelling properties, from supergelation to the absence of gelling ability. The utilization of the Hansen solubility parameters allows for observing clear relationships between the gelled solvents and critical gelation concentrations. By evaporating the solvents from the organogels, xerogel materials were prepared and systematically studied by means of optical and electron microscopy as well as SHG microscopy. These studies demonstrate the critical role of the solvent over material structuring and allow generalizing the approach exploiting organogelation as a structuring tool to spontaneously organize push-pull chromophores into SHG-active materials.
RESUMO
An organogelator based on the Disperse Red nonlinear optical chromophore was synthesized according to a simple and efficient three-step procedure. The supramolecular gel organization leads to xerogels which display a spontaneous second harmonic generation (SHG) response without any need for preprocessing, and this SHG activity appears to be stable over several months. These findings, based on an intrinsic structural approach, are supported by favorable intermolecular supramolecular interactions, which promote a locally non-centrosymmetric NLO-active organization. This is in sharp contrast with most materials designed for SHG purposes, which generally require the use of expensive or heavy-to-handle external techniques for managing the dipoles' alignment.
RESUMO
Chromophores where a polyenic spacer separates a 4H-pyranylidene or benzothiazolylidene donor and three different butenolide nitriles have been synthesized and characterized. The role of 2(5H)-furanones as acceptor units on the polarization and the second-order nonlinear (NLO) properties has been studied. Thus, their incorporation gives rise to moderately polarized structures with NLO responses that compare favorably to those of related compounds featuring more efficient electron-withdrawing moieties. Derivatives of the proaromatic butenolide PhFu show the best nonlinearities. Benzothiazolylidene-containing chromophores present less alternated structures than their pyranylidene analogues, and, unlike most merocyanines, the degree of charge transfer does not decrease on lengthening the π-bridge.
RESUMO
Chromophores bearing a 2-dicyanomethylenethieno[3,2-b]thiophene moiety in their quinoidal form have been synthesized, exploring for the first time the reactivity of this system towards aldehydes. Their ground state polarization and linear and second-order nonlinear optical (NLO) properties have been determined by a combined experimental and theoretical study, and compared to those of analogous compounds featuring an aromatic thienothiophene unit. Due to the gaining of aromaticity, quinoid systems have been found to display more polarized electronic ground states and higher NLO responses with respect to their aromatic counterparts.
RESUMO
Hole-transporting materials (HTMs) have demonstrated their crucial role in promoting charge extraction, interface recombination, and device stability in perovskite solar cells (PSCs). Herein, we present the synthesis of a novel dopant-free spiro-type fluorine core-based HTM with four ethoxytriisopropylsilane groups (Syl-SC) for inverted planar perovskite solar cells (iPSCs). The thickness of the Syl-SC influences the performance of iPSCs. The best-performing iPSC is achieved with a 0.8 mg/mL Syl-SC solution (ca. 15 nm thick) and exhibits a power conversion efficiency (PCE) of 15.77%, with Jsc = 20.00 mA/cm2, Voc = 1.006 V, and FF = 80.10%. As compared to devices based on PEDOT:PSS, the iPSCs based on Syl-SC exhibit a higher Voc, leading to a higher PCE. Additionally, it has been found that Syl-SC can more effectively suppress charge interfacial recombination in comparison to PEDOT:PSS, which results in an improvement in fill factor. Therefore, Syl-SC, a facilely processed and efficient hole-transporting material, presents a promising cost-effective alternative for inverted perovskite solar cells.
RESUMO
Multichromophoric calix[4]arenes with two or four disperse red one (DR1) moieties linked to the lower rim have been synthesized. The second-order nonlinear optical activity was measured by using the electric-field-induced second-harmonic generation technique and there was a nearly linear increase of the µß value with the number of chromophores in the molecule without affecting the charge-transfer absorption wavelength. The effect that the number of DR1 units plays on the hyperpolarizability, the dipole moment, and the absorption maxima has been also studied by using quantum chemical calculations. It was found that it was necessary to synthesize multichromophores with distant chromophores to obtain large nonlinear optical responses.
RESUMO
A series of new 4H-pyran-4-ylidene donor-based chromophores with a thiophene ring in the spacer has been synthesized. The linear and nonlinear optical (NLO) properties of these compounds have been determined and compared with the results of computational calculations. The position of the thiophene ring proved essential to optimize the figure of merit µß, with the best results obtained when the heterocyclic system was closer to the donor moiety.
RESUMO
The formal [2 + 2] cycloaddition-cycloreversion (CA-CR) between 4-ethynyl-N,N-dimethylaniline and polyenic Donor-π-Acceptor (D-π-A) systems takes place to yield compounds bearing two donors and one acceptor. Structural, linear and second-order nonlinear optical (NLO) properties of the new molecules reveal the stronger polarization of these systems when compared to analogous merocyanines lacking the dimethylaminophenyl (DMA) ring.
Assuntos
Alcinos/química , Polienos/química , Ciclização , Elétrons , Modelos Moleculares , Estrutura MolecularRESUMO
Push-pull compounds, in which a proaromatic electron donor is conjugated to a 2-dicyanomethylenethiazole acceptor, have been prepared, and their properties compared to those of model compounds featuring an aromatic donor. A combined experimental (X-ray diffraction, (1) Hâ NMR, IR, Raman, UV/Vis, nonlinear optical (NLO) measurements) and theoretical study reveals that structural and solvent effects determine the ground-state polarisation of these merocyanines: whereas 4H-pyran-4-ylidene- and 4-pyridylidene-containing compounds are zwitterionic and 1,3-dithiol-2-ylidene derivatives are close to the cyanine limit, anilino-derived merocyanines are essentially neutral. This very large range of intramolecular charge transfer (ICT) gives rise to efficient second-order NLO chromophores with µß values ranging from strongly negative to strongly positive. In particular, pyranylidene derivatives are unusual in that they show an increase in the degree of ICT on lengthening the π-spacer, a feature that lies behind the very large negative µß values they display. The linking of the formally quinoidal 2-dicyanomethylenethiazole moiety to proaromatic donors seems a promising approach towards the optimisation of zwitterionic NLO chromophores.
RESUMO
A simple synthesis of dipolar one- and two-dimensional chromophores bearing two or three 4H-pyran-4-ylidene moieties is reported. Whereas the pyranylidene fragments acting as donors are proaromatic, the spacer one is not. In the linear derivatives, chain elongation gives rise to a sharp increase in the second order nonlinear optical responses, but some V-shaped derivatives display first hyperpolarizabilities (beta) lower than those of their linear analogues. This uncommon feature lends experimental support to previous theoretical studies on the relative contribution and sign of the beta-tensor components.
RESUMO
Merocyanines where a polyenic spacer separates a 4H-pyran-4-ylidene moiety and different strong organic acceptors have been synthesized. According to NMR studies and X-ray diffraction data, these compounds have weakly alternated structures and remarkably zwitterionic ground states, with a partial aromatic character that is compared to those of other pyran derivatives. The proaromaticity of the 4H-pyran-4-ylidene donor lies behind the cyanine-like behavior and low (positive or negative) second-order optical nonlinearities of the shorter derivatives. On the other hand, lengthening the pi-spacer gives rise to rapidly increasing mubeta(1907) values up to 17,400 x 10(-48) esu.
RESUMO
A short, high-yielding route to omega-dithiafulvenylpolyenals (1) via the corresponding iminium salts (2) and starting from trimethyl-1,3-dithiolium tetrafluoroborate is reported. The Knoevenagel reactions of either 1 or 2 with isoxazolone-containing acceptors afford merocyanines 7 and 9, in a process that is often accompanied by a vinylene-shortening side reaction. Experimental and theoretical studies reveal that compounds 7 and 9, featuring two proaromatic end groups, are strongly polarized and show good second-order nonlinear optical responses.
RESUMO
4H-Pyranylidene-containing push-pull chromophores built around a bithiophene (BT) π relay or a rigidified thiophene-based unit, namely cyclopenta[1,2-b:3,4-b']dithiophene (CPDT) or dithieno[3,2-b:2',3'-d]pyrrole (DTP), have been synthesized and characterized. The effect of these different relays on the polarization and the second-order nonlinear optical (NLO) properties has been studied. For the sake of comparison, the corresponding reported dithieno[3,2-b:2',3'-d]thiophene (DTT) derivatives have also been included in the discussion. Replacement of the BT core by a rigidified unit (CPDT, DTP) leads to more polarized systems. Calculated NBO charges and electrochemical measurements show that dithienopyrrole has a remarkable donor character that allows an important charge transfer between the donor and the acceptor. The influence of the rigidification of the BT relay on the NLO responses depends on the acceptor strength. For the weakest acceptor used (thiobarbituric acid), passing from the BT relay to the rigidified units always involves an increase in the µß0 figure of merit. Nevertheless, for the strongest acceptor (2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF)), a slight increase in µß0 with respect to the BT chromophore is only observed for the DTP derivative. Thus, rigidification of the BT core is not enough to improve the second-order nonlinearity and the incorporation of a DTP moiety has proven to be the most efficient approach for this purpose.
RESUMO
[reaction: see text] Novel D-pi-A NLO-phores based on the 1,3-dithiol-2-ylidene donor and the thiobarbituric acceptor moieties have been prepared. Modification of the length and rigidity of the pi-spacer allows the first systematic study of the second-order nonlinear optical properties of doubly proaromatic merocyanines. The pi-electron donor efficiency of the 1,3-dithiol-2-ylidene group is superior to that of the tetrathiafulvalenyl group.
RESUMO
Replacement of the tricyanofuran (TCF) acceptor by its stronger analogue CF 3-TCF results in decreased second-order optical nonlinearities in merocyanines bearing a proaromatic 1,3-dithiole donor. The TCF-containing derivatives display exceptionally high mu beta values up to 31,000 x 10(-48) esu, unprecedented for 1,3-dithiole-based NLO-phores.
RESUMO
Polyenic nonlinear optic (NLO)-phores with a proaromatic 1,4-dithiafulvene electron donor and the little explored 1,1,3-tricyano-2-phenylpropene acceptor have been synthesized. Their configurational and conformational features, ground state polarization, and linear and nonlinear optical properties have been determined experimentally and theoretically, and the results are compared to those of tetrathiafulvalene-related derivatives. The newly prepared compounds show close to optimal bond length alternation values for maximizing the first molecular hyperpolarizability, and one of them displays the highest mu beta0 value ever reported for a dithiafulvene-based NLO-phore. The first example of a dithiafulvenylmethylene transfer reaction is also reported.
RESUMO
The Raman spectra of a series of push-pull molecules containing probenzenoid or quinoid spacers which are substituted with 1,3-dithiol-2-ylidene as donor and dicyano-methylene or barbituric acid as acceptors have been analyzed. The experimental spectra have been assigned and interpreted according to density functional theory calculations. Correlations between the Raman spectra of the isolated spacers and of the substituted molecules have been done. Raman bands in the 1620-1560 cm-1 interval provide vibrational markers of the quinoid<-->aromatic structural evolution. This finding is supported by a careful inspection of geometrical parameters, namely, bond length alteration data and particular bond distances. As a result, the peak positions and relative intensities of these Raman features can be used to evaluate the benzenoid character of the spacer as a function of the donor/acceptor substitution pattern. This paper shows that Raman spectroscopy is a powerful spectroscopic tool for the analysis of the conjugational properties (i.e., intramolecular donor-->acceptor charge transfer) of new organic materials.
RESUMO
In this paper, we describe the second-order nonlinear optical properties of a series of 1,3-dithiole-based electron donor-acceptor systems incorporating proaromatic donor and spacer groups. Modification of the proaromaticity of the quinoid spacer gives rise to NLO-phores with mubeta values ranging from -2000 x 10(-)(48) esu to +3000 x 10(-)(48) esu. Quite surprisingly, compounds with a p-benzoquinoid spacer and a strong acceptor group show negative mubeta values, usually associated to zwitterionic ground states, and yet they are largely quinoid, as evidenced by crystallographic data and theoretical calculations. Progressive benzoannulation of the spacer and introduction of alkylsulfanyl substituents on the dithiole donor unit result in a shift to more positive mubeta values. DFT and ab initio calculations verify these empirical trends.