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Quantum emitters in two-dimensional layered hexagonal boron nitride are quickly emerging as a highly promising platform for next-generation quantum technologies. However, the precise identification and control of defects are key parameters to achieve the next step in their development. We conducted a comprehensive study by analyzing over 10,000 photoluminescence emission lines from liquid exfoliated hBN nanoflake samples, revealing 11 narrow sets of defect families within the 1.6 to 2.2 eV energy range. This challenges hypotheses of a random energy distribution. We also reported averaged defect parameters, including emission line widths, spatial density, phonon side bands, and Franck-Condon-related factors. These findings provide valuable insights into deciphering the microscopic origin of emitters in hBN hosts. We also explored the influence of the hBN host morphology on defect family formation, demonstrating its crucial impact. By tuning the flake size and arrangement, we achieve selective control of defect types while maintaining high spatial density. This offers a scalable approach to defect emission control, diverging from costly engineering methods. It emphasizes the significance of the morphological aspects of hBN hosts for gaining insights into defect origins and expanding their spectral control.
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A series of novel V-shaped quinoxaline, [1,2,5]oxadiazolo[3,4-b]pyrazine and [1,2,5]thiadiazolo[3,4-b]pyrazine push-pull derivatives with 2,4'-biphenylene linker were designed and their electrochemical, photophysical and nonlinear optical properties were investigated. [1,2,5]Oxadiazolo[3,4-b]pyrazine is the stronger electron-withdrawing fragment as shown by electrochemical, and photophysical data. All compounds are emissive in a solid-state (from the cyan to red region of the spectrum) and quinoxaline derivatives are emissions in DCM solution. It has been found that quinoxaline derivatives demonstrate important solvatochromism and extra-large Stokes shifts, characteristic of twisted intramolecular charge transfer excited state as well as aggregation induced emission. The experimental conclusions have been justified by theoretical (TD-)DFT calculations.
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A series of four V-shaped methylpyrimidinium salts bearing diphenylamino-electron-donating groups appended at various pyrimidine positions were designed. These chromophores were obtained by regioselective N(1) monomethylation by methyl methanesulfonate of the pyrimidine core. Linear optical properties were studied experimentally and electronic properties were further completed by (TD)-DFT calculations. The second-order nonlinear optical (NLO) properties were also studied using electric field induced second harmonic generation (EFISH) method in chloroform, and all pyrimidinium salts exhibited µß0 >1000×10-48 â esu. The 2,4-disubstituted pyrimidinium core is preferred over 4,6-disubstitution as it enhances the NLO response and increases the dipole moment. (E,E)-2,4-Bis[4-(diphenylamino)styryl]-1-methylpyrimidin-1-ium methanesulfonate appears to be the best NLO-phore in chloroform in the series (µß0 =2500×10-48 â esu) and a figure of merit µß0 /MW=3.4 10-48 â esu mol g-1 .
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A series of four D-(π-Pt-π-A)2 new V-shaped binuclear platinum(ii) complexes bearing a diphenylpyranylidene ligand as a pro-aromatic donor group (D) and various electron-attracting groups (A) separated by platinum bis-acetylide fragments have been synthesized, characterized and studied for their electrochemical, photophysical and second-order nonlinear optical (NLO) properties. The nonlinear optical properties of these complexes have been determined by using the Electric-Field-Induced Second Harmonic (EFISH) generation technique, and their optical properties have been rationalized by Time-Dependent Density Functional Theory (TD-DFT) calculations relying on a range-separated hybrid. All complexes display positive µß0 values. In addition, the second-order NLO responses of the complexes could be easily modulated by incorporating various end-capped electron-attracting groups, namely malononitrile, indane-1,3-dione, pyrimidine and pyrimidinium. Remarkably, complex 7 bearing a pyrimidinium fragment displays the highest µß0 value among all the complexes of this series. Its NLO response is twice as high as that of the mononuclear analogue complex RD2, which has been confirmed both experimentally and theoretically.
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A series of D-π-A chromophores based on allylidenemalononitrile electron-withdrawing group was designed. The influence of the amino-electron-donating group on the photophysical properties was studied. These compounds, highly thermally stable, exhibit orange-red emission in solution and in solid state. The experimental results have been rationalized by theoretical DFT calculations. The second order nonlinear optical properties were also studied using the electric field induced second harmonic generation (EFISH) method.
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Herein we report the synthesis and characterization of a new series of styryl-based push-pull dyes containing a free amino group and their Schiff base derivatives. The dyes include the dicyanomethylene group as an acceptor and different para-substituted alkylamines as donors. Morever as a proton-sensitive group a pyridin-2-yl substituent was attached to the para-position of the phenyl moiety in both series of compounds. The photophysical properties of the dyes were examined in various solvents with different polarities and showed absorption in the visible region and green-red emission with low quantum yields. The absorption and the emission maxima were shifted bathocromically by increasing the solvent's polarity. However, there was no correlation with the polarity parameters of the solvents. The pH-sensitive properties of all prepared Schiff bases were examined against TBAOH in DMSO, via deprotonation of the OH group in the salicylidene moiety and their reverse protonation was also investigated using TFA. The Schiff bases exhibited a bathochromic shift upon the addition of TBAOH to their solutions in DMSO. Therefore, they showed potential to be utilized as colorimetric and luminescence pH sensors. The second-order nonlinear optical (NLO) responses of the dyes were measured by the electric field-induced second harmonic (EFISH) generation method. The highest µß values were obtained for the dyes bearing the julolidine donor as 1430 × 10-48 esu (for free amino derivative) and 1950 × 10-48 esu (for Schiff base derivative), respectively. The structural and electronic properties of the dyes as well as their NLO properties were further studied using DFT calculations. The thermal stabilities of all dyes were evaluated by thermogravimetric analysis (TGA). The TGA data showed that all dyes were thermally stable up to 250 °C.
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The present work describes the one-pot synthesis and electrochemical, photophysical and second-order nonlinear optical (NLO) properties of a series of dipolar π-delocalized Ru(ii) dialkynyl complexes. The eight new asymmetrical D-π-Ru-π-A push-pull chromophores incorporate pyranylidene ligands as pro-aromatic donor groups (D) and formaldehyde, indane-1,3-dione, pyrimidine or pyrimidinium as electron-attracting groups (A) separated by ruthenium bis-acetylide fragments and π-conjugated linkers. The second-order nonlinear optical (NLO) properties of all eight complexes were determined by the Electric-Field-Induced Second Harmonic generation (EFISH) technique (operating at 1907 nm), and were compared to those of their purely organic analogs. All investigated compounds (organic and organometallic) exhibited positive µß values, which dramatically increased for the complexes due to the presence of ruthenium in the π-conjugated core. The second-order NLO response could also be easily modulated by changing the nature of alkynyl substituents. The most promising ruthenium complexes 7 and 8 of the series with the pyrimidinium fragment displayed µß values of 14 000 × 10-48 esu. The effect of structural modifications on the redox and spectroscopic properties of the complexes was also studied. The intramolecular charge transfer (ICT) occurring through the ruthenium center of the push-pull σ-dialkynyl complexes was investigated by combining experimental and theoretical data.
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The synthesis of a series of push-pull derivatives bearing triphenylamine electron-donating group, cyclopenta[c]thiophen-4,6-dione electron acceptor and various π-linkers including (hetero)aromatic fragments is reported. All target chromophores with systematically varied π-linker structure were further investigated by electrochemistry, absorption measurements, and EFISH experiments in conjunction with DFT calculations. Based on electrochemical and photophysical measurements, when a polarizable 2,5-thienylene moiety is embedded into the chromophore π-backbone the highest intramolecular charge transfer (ICT) is observed. Benzene, pyrimidine, and pyridazine derivatives exhibit lower polarizability and extent of the ICT across these π-linkers. The elongation of the π-conjugated system via additional ethenylene linker results in a significant reduction of the HOMO-LUMO gap and an enhancement of the NLO response. Whereas it does not significantly influence electrochemical and linear optical properties, the orientation of the pyrimidine ring seems to be a key parameter on the µß value due to significant variation of the dipolar moment (µ) value. In 2a and 2c, pyrimidine is oriented to behave as an acceptor and thus generate dipolar molecule with µ above 5 D, whereas in 2b and 2d ground state dipole moment is significantly reduced. This study seems to indicate a high aromaticity of pyrimidine and pyridazine derivatives, close to the benzene analogues and significantly higher than thiophene analogues.
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In this article, we describe the synthesis, redox characteristics, and linear and nonlinear optical (NLO) properties of seven new unsymmetrical push-pull diacetylide platinum-based complexes. These D-π-Pt-π-A complexes incorporate pyranylidene ligands as pro-aromatic donor groups (D), diazine rings as electron-withdrawing groups (A), and various aromatic fragments (styryl or thienylvinyl) as π-linkers separating the platinum diacetylide unit from the donor and the acceptor groups. This is one of the first examples of push-pull chromophores incorporating a platinum center in the π-conjugated core. The NLO properties of these complexes were compared with those of their purely organic analogues. All compounds (organic and organometallic) exhibited positive µß values, which dramatically increased upon methylation of the pyrimidine fragment. However, this increase was even more significant in the complexes due to the presence of platinum in the π-conjugated core. The effects of the linker on the redox and spectroscopic properties of the complexes are also discussed. In addition, DFT calculations were performed in order to gain further insight into the intramolecular charge transfer (ICT) occurring through the platinum center.
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We present experimental and theoretical study of the interaction of Light Induced Self-Written (LISW) waveguides in photopolymers. We show that the diffusion of the monomer controls the refractive index distribution. Consequently it influences the interaction between the LISW channels allowing the observation of anti-crossing behavior or the propagation of an array of non interacting LISW waveguides.
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Highly stable and highly soluble push-pull heptamethine hemicyanines based on the tricyanofuran electron-accepting group can be prepared on a 15â g scale. The compounds display giant second-order nonlinear figure of merit, µß of up to 31,000×10(-48)â esu, and lead to a poled material with a second-order nonlinear response, r33 of 90â pm V(-1) at 1.06â µm.
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A set of linear and dissymmetric BODIPY-bridged push-pull dyes are synthesized. The electron-donating substituents are anisole and dialkylanilino groups. The strongly electron-accepting moiety, a 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) group, is obtained by insertion of an electron-rich ethyne into tetracyanoethylene. A nonlinear push-pull system is developed with a donor at the 5-position of the BODIPY core and the acceptor at the 2-position. All dyes are fully characterized and their electrochemical, linear and nonlinear optical properties are discussed. The linear optical properties of dialkylamino compounds show strong solvatochromic behavior and undergo drastic changes upon protonation. The strong push-pull systems are non-fluorescent and the TCBD-BODIPY dyes show diverse photochemistry and electrochemistry, with several reversible reduction waves for the tetracyanobutadiene moiety. The hyperpolarizability µß of selected compounds is evaluated using the electric-field-induced second-harmonic generation technique. Two of the TCBD-BODIPY dyes show particularly high µß (1.907 µm) values of 2050 × 10(-48) and 5900 × 10(-48) esu. In addition, one of these dyes shows a high NLO contrast upon protonation-deprotonation of the donor residue.
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The mixed-ligand complexes [M(II)(Et2dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et2dazdt = N,N'-diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1-3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P-1), and two independent molecular entities are present in the unit cell. These entities differ in the orientation of the ethyl substituents with respect to the epta-atomic ring. In the C2S2MS2C2 dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the M-S bond distances involving the two ligands are similar, while the C-S bond distances in the C2S2 units exhibit a significant difference in Et2dazdt (dithione) and mnt (dithiolato) ligands. 1-3 show in the visible region one or two moderately strong absorption peaks, having ligand-to-ligand charge-transfer (CT) character with some contribution of the metal, and show negative solvatochromism and molecular quadratic optical nonlinearity, which was determined by the EFISH (electric-field-induced second-harmonic generation) technique. These complexes are redox active and show two reversible reduction waves and one irreversible oxidation wave. Theoretical calculations based on DFT and TD-DFT calculations on complexes 1-3 as well as on [Pt(Bz2pipdt)(mnt)] (4) and [Pt(Bz2pipdt)(dmit)] (5) highlight the factors which affect the optical properties of these second-order redox-active NLO chromophores. Actually, the torsion angle of the dithione system (δ2) inversely correlates either with the oscillator strengths of the main transition of the complexes or with their beta values. The high beta value of 5 can be attributed both to its lowest torsion angles and to the extent of the π system of its dithiolate ligand, dmit.
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The nonlinear properties and the photophysical behavior of two π-conjugated chromophores that incorporate an electron-deficient pyrimidine core (A) and γ-methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes' scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end-groups. This latter structural parameter also has a strong influence on the excited-state dynamics, which leads to a very efficient fluorescence quenching.
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Colorantes Fluorescentes/síntesis química , Piranos/química , Pirimidinas/química , Colorantes Fluorescentes/química , Cinética , Conformación Molecular , Teoría Cuántica , Espectrofotometría UltravioletaRESUMEN
We report on the demonstration of liquid organic dye lasers based on 9-(2-ethylhexyl)carbazole (EHCz), so-called liquid carbazole, doped with green- and red-emitting laser dyes. Both waveguide and Fabry-Perot type microcavity fluidic organic dye lasers were prepared by capillary action under solvent-free conditions. Cascade Förster-type energy transfer processes from liquid carbazole to laser dyes were employed to achieve color-variable amplified spontaneous emission and lasing. Overall, this study provides the first step towards the development of solvent-free fluidic organic semiconducting lasers and demonstrates a new kind of optoelectronic applications for liquid organic semiconductors.
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Colorantes/química , Rayos Láser , Compuestos Orgánicos/química , Refractometría/instrumentación , Soluciones/química , Resonancia por Plasmón de Superficie/instrumentación , Diseño de Equipo , Análisis de Falla de Equipo , SolventesRESUMEN
We present the inscription of a Light Induced Self-Written (LISW) waveguide in a 4-cyano-4'-pentylbipheny (5CB) doped photopolymer. The dynamic reorientation of the 5CB molecules in the material under applied electric field leads to birefringence in LISW waveguide and thus allows the control of the phase of the guided mode.
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Compuestos de Bifenilo/química , Compuestos de Bifenilo/efectos de la radiación , Impresión Molecular/métodos , Nitrilos/química , Nitrilos/efectos de la radiación , Refractometría/instrumentación , Resonancia por Plasmón de Superficie/instrumentación , Telecomunicaciones/instrumentación , Campos Electromagnéticos , Diseño de Equipo , Análisis de Falla de Equipo , Luz , Polímeros/química , Polímeros/efectos de la radiación , Dispersión de Radiación , Propiedades de Superficie/efectos de la radiaciónRESUMEN
A new series of push-pull arylvinyldiazines has been efficiently prepared by aldol condensation between the appropriate methyldiazine and aromatic aldehyde. The optical absorption and emission properties of these chromophores were studied in different solvents and media. These compounds act as polarity sensors with a strong positive emission solvatochromism. This behavior suggests a highly polar emitting state, which is characteristic of compounds that undergo an internal charge transfer upon excitation. These molecules also exhibit halochromic properties and are potential colorimetric and luminescence pH sensors. The second-order nonlinear properties have been investigated for some of the compounds, and large and positive µß are obtained, in particular, for pyrimidine derivatives.
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Pirimidinas/química , Compuestos de Vinilo/química , Compuestos de Vinilo/síntesis química , Absorción , Colorimetría , Luminiscencia , Fotones , Espectrofotometría UltravioletaRESUMEN
We have performed multi-photon image reconstructions as well as polarization state analyses inside an artery wall affected by atherosclerosis to investigate the changes in collagen structure. Mice, either healthy or affected by spontaneous atherosclerosis, have been used for this purpose. A two-photon imaging system has been used to investigate atherosclerotic lesions in the ascending aorta of mice. Second harmonic imaging has been performed alternatively on healthy samples and on affected region. The reconstructed images show that the spatial distribution of the collagen network seems disorganized by the disease. The polarization state studies reveal however that the apparent disorganization of the collagen is related to its spatially diffuse distribution and that the internal structure of the collagen fibers is not affected by the disease. In addition, a theoretical simulation of the second harmonic polarization states shows that they are consistent with the known 3D structure of the collagen network.
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Aterosclerosis/diagnóstico , Animales , Aorta/patología , Arterias/fisiopatología , Aterosclerosis/patología , Colágeno/química , Colágeno/metabolismo , Modelos Animales de Enfermedad , Elastina/metabolismo , Humanos , Procesamiento de Imagen Asistido por Computador , Ratones , Ratones Endogámicos C57BL , Ratones Noqueados , Microscopía Confocal/métodos , Microscopía de Polarización/métodos , Modelos Estadísticos , Distribución NormalRESUMEN
Synthesis, characterization, NLO properties, and theoretical studies of the mixed-ligand dithiolene complexes of the nickel triad [M(II)(Bz(2)pipdt)(mnt)] (Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione, mnt = maleonitriledithiolato, M(II) = Ni, 1, Pd, 2, Pt, 3) are reported. Molecular structural characterization of 1-3 points out that four sulfur atoms are in a slightly distorted square-planar geometry. While the M-S bond distances are only slightly different, comparison of the C-C and C-S bonds in the C(2)S(2)MS(2)C(2) core allows us to point out a significant difference between the C-C and the C-S distances in Bz(2)pipdt and mnt. These findings suggest assigning a dithiolato character to mnt (pull ligand) and a dithione one (push ligand) to Bz(2)pipdt. Cyclic voltammetry of 1-3 exhibits two reversible reduction waves and a broad irreversible oxidation wave. These complexes are characterized in the visible region by a peak of moderately strong intensity, which undergoes negative solvatochromism. The molecular quadratic optical nonlinearities were determined by the EFISH technique, which provided the following values µß(λ) (10(-48) esu) = -1436 (1), -1450 (2), and -1950 (3) converted in µß(0) (10(-48) esu) = -463 (1), -684 (2), and -822 (3), showing that these complexes exhibit large negative second-order polarizabilities whose values depend on the metal, being highest for the Pt compound. DFT and TD-DFT calculations on 1-3 allow us to correlate geometries and electronic structures. Moreover, the first molecular hyperpolarizabilities have been calculated, and the results obtained support that the most appealing candidate as a second-order NLO chromophore is the platinum compound. This is due to (i) the most extensive mixture of the dithione/metal/dithiolato orbitals, (ii) the influence of the electric field of the solvent on the frontier orbitals that maximizes the difference in dipole moments between the excited and the ground state, and (iii) the largest oscillator strength in the platinum case vs nickel and palladium ones.
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The synthesis and full characterization of the redox-active nickel triad mixed-ligand dithiolene complexes based on Bz(2)pipdt = 1,4-dibenzylpiperazine-3,2-dithione and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate ligands are reported. These complexes show a reversibly bleacheable solvatochromic peak and a remarkably high negative molecular first hyperpolarizability, whose values depend on the metal being highest for the platinum(II) compound.