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Item type:Publication, Access status: with files , Transition-metal azo Schiff base complexes: nonlinear optics across solutions, thin films and nanocomposites(Wiley, 2025-10-24); ; ; ; This paper investigates the nonlinear optical (NLO) properties of azo-based Schiff base ligand and its corresponding complexes incorporating Cu(II) and Zn(II) metal cations, designed upon the previous synthesis work. Both 2nd and 3rd order NLO properties are examined, with a particular focus on their potential for optoelectronic and photonic applications. The Z-scan technique is employed to analyze NLO refraction and NLO absorption in solution. All samples exhibit positive NLO phenomena, with Zn(L)2 showing the highest values (𝝌(3) = 27.95 × 10−22 m2 V−2, 𝜸 = 54.44 × 10−47 m5 V−2), attributed to enhanced ligand-to-metal charge transfer (LMCT). Additionally, thin films deposited via the spin coating method undergo 3rd order NLO analysis through the Maker fringe technique. THG analysis further confirms superior 3rd order NLO performance in Zn(L)2, exceeding several benchmark transition-metal complexes. 2nd order NLO properties are also explored in hybrid nanocomposites designed from Zn(L)2 embedded in nanoporous pSiO2 membrane. This structure exhibits anisotropic SHG behavior, with 𝝌 (2) = 0.11 pm V−1 under s-p polarization, suggesting polarization confinement within nanochannels. The results clearly demonstrate that transition-metal azo Schiff base complexes, particularly Zn(L)2, exhibit strong NLO responses, positioning them as potential candidates for applications in all-optical switching and frequency conversion.Publicationtype: Journal Article22 17 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Controlling organic semiconductor self-assembly through cylindrical nanoconfinement(American Chemical Society (ACS), 2025-09-30); ; ; ; Controlling the self-assembly of organic semiconductors at the nanoscale is critical for advancing high-performance electronic and photonic devices, yet remains challenging due to their intrinsic anisotropic crystallization and sensitivity to processing conditions. Here, we demonstrate that cylindrical nanoconfinement within anodic aluminum oxide membranes provides a versatile platform to precisely tune the molecular orientation and phase behavior of the prototypical organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8). Combining temperature-dependent high-resolution synchrotron X-ray scattering with optical birefringence measurements, we uncover that confinement geometries (pore diameters 25–180 nm) and surface chemistry govern the emergence of distinct smectic A textures, featuring molecular layers either parallel or perpendicular to the pore axis. The competition between axial and radial smectic layering is modulated by pore size, surface hydrophilicity, and thermal history, enabling reversible control over domain orientations and transitions between liquid crystalline and crystalline states. Notably, nanoconfinement stabilizes the smectic phase over an expanded temperature range compared to bulk, while inducing complex multi-domain configurations owing to geometric constraints and anchoring conditions. Our results elucidate fundamental mechanisms by which anisotropic nanoscale confinement directs the self-organization of highly conjugated organic molecules, with implications for optimizing directional charge transport and anisotropic optical responses in organic–inorganic hybrid nanoarchitectures. This study establishes nanoconfinement as a powerful strategy to engineer morphology and functional properties in organic semiconducting materials with nanoscale precision.Publicationtype: Preprint45 18 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Self-assembly of bent-core nematics in nanopores(American Chemical Society (ACS), 2025-06-17); ; ; ; Bent-core nematic liquid crystals exhibit unique properties, including giant flexoelectricity and polar electro-optic responses, making them ideal for energy conversion and electro-optic applications. When confined in nanopores, they can stabilize chiral nanostructures, enhance polar order, and enable defect-driven switching -- offering potential in nanofluidics, sensing, and adaptive optics. Here we examine the thermotropic ordering of the bent-core dimer CB7CB confined in anodic aluminum oxide (AAO) and silica membranes with precisely engineered cylindrical nanochannels -- ranging from just a few nanometers to several hundred nanometers. These well-aligned nanochannels enable high-resolution polarimetry studies of optical anisotropy, revealing how geometric confinement affects molecular organization and phase behavior. Under weak confinement, CB7CB forms a layered heterophase structure, with nematic, splay-bent, and twist-bent heliconical phases likely arranged concentrically. As confinement increases, a Landau-de Gennes analysis shows that ordered phases are suppressed, leaving only a paranematic phase under strong spatial constraints. Remarkably, temperature-dependent changes in optical birefringence under confinement closely resemble those seen under applied electric fields, revealing a parallel between geometric and electro-optic effects. Overall, our work demonstrates how nanoconfinement allows one to systematically tailor the self-assembly and optical behavior of bent-core nematics, enabling novel functionalities in responsive and anisotropic materials.Publicationtype: Preprint18 13 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Self-assembly of bent-core nematics in nanopores(Wiley, 2025); ; ; Bent-core nematic liquid crystals exhibit unique properties, including giant flexoelectricity and polar electro-optic responses, making them ideal for energy conversion and electro-optic applications. When confined in nanopores, they can stabilize chiral nanostructures, enhance polar order, and enable defect-driven switching – offering potential in nanofluidics, sensing, and adaptive optics. The thermotropic ordering of the bent-core dimer CB7CB confined in anodic aluminum oxide (AAO) and silica membranes with precisely engineered cylindrical nanochannels – ranging from just a few nanometers to several hundred nanometers–is examined. These well-aligned nanochannels enable high-resolution polarimetry studies of optical anisotropy, revealing how geometric confinement affects molecular organization and phase behavior. Under weak confinement, CB7CB forms a layered heterophase structure, with nematic, splay-bent, and twist-bent heliconical phases likely arranged concentrically. As confinement increases, a Landau-de Gennes analysis shows that ordered phases are suppressed, leaving only a paranematic phase under strong spatial constraints. Remarkably, temperature-dependent changes in optical birefringence under confinement closely resemble those seen under applied electric fields, revealing a parallel between geometric and electro-optic effects. Overall, this work demonstrates how nanoconfinement allows one to systematically tailor the self-assembly and optical behavior of bent-core nematics, enabling novel functionalities in responsive and anisotropic materials.Publicationtype: Journal Article24 13 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Synthesis, nanocrystalline morphology, lattice dynamics and nonlinear optics of mesoporous SiO2&LiNbO3 nanocomposite(Springer, 2024-10-16); ; ; ; We demonstrate a hybrid nanocomposite combining mesoporous silica, pSiO2, as a host medium and guest lithium niobate LiNbO3 nanocrystals embedded into tubular silica nanochannels by calcination of the precursor mixed solution of lithium and niobium salts. High-resolution transmission electron microscopy, X-ray diffraction and Raman scattering techniques reveal trigonal LiNbO3 nanocrystals within the pSiO2 nanochannels, indicating their random texture morphology. Annealing at high temperatures (950∘C) during calcination also leads to partial crystallization of the pSiO2 matrix with the formation of trigonal α-SiO2 nanocrystals. The Raman microscopy analysis of the pSiO2:LiNbO3 nanocomposite reveals three structural crystalline phases, α-SiO2, LiNbO3 and a mixed phase which involves the α-SiO2 phase of host membrane and LiNbO3 nanocrystals embedded into the membrane. The finite size of the LiNbO3 nanocrystals results in specific features of the LO-TO phonon frequency splitting, which are investigated by Raman microscopy. In the transmission geometry, the second harmonic generation emission exhibits no Maker fringes and is characterized by a broad angular diagram of diffusely scattered light. The second harmonic generation response is independent of the polarization direction of the incident pump light, thus indicating a spatial isotropy of the nonlinear optical conversion in the pSiO2:LiNbO3 composite, consistent with the randomly oriented textural morphology of the deposited LiNbO3 nanocrystals. The contribution of the guest LiNbO3 nanocrystals to the second harmonic generation effect was found to be strongly dominant compared to the partially crystallized host pSiO2 matrix. The nanocomposite pSiO2:LiNbO3 membrane, set in the 90∘ nonlinear optical geometry, shows unusually high diffusely transmitted second harmonic generation light (back-reflected emission), apparently supported by internal light reflection from the tubular nanochannel network. Despite the fundamental interest, the revealed anomalous back-reflected second harmonic generation emission from pSiO2:LiNbO3 nanocomposite membranes expands the prospects for their photonic and nonlinear optical applications.Publicationtype: Journal Article19 21 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Self-assembly of ionic superdiscs in nanopores(American Chemical Society (ACS), 2024-06-04); ; ; ; Discotic ionic liquid crystals (DILCs) consist of self-assembled superdiscs of cations and anions that spontaneously stack in linear columns with high one-dimensional ionic and electronic charge mobility, making them prominent model systems for functional soft matter. Compared to classical nonionic discotic liquid crystals, many liquid crystalline structures with a combination of electronic and ionic conductivity have been reported, which are of interest for separation membranes, artificial ion/proton conducting membranes, and optoelectronics. Unfortunately, a homogeneous alignment of the DILCs on the macroscale is often not achievable, which significantly limits the applicability of DILCs. Infiltration into nanoporous solid scaffolds can, in principle, overcome this drawback. However, due to the experimental challenges to scrutinize liquid crystalline order in extreme spatial confinement, little is known about the structures of DILCs in nanopores. Here, we present temperature-dependent high-resolution optical birefringence measurement and 3D reciprocal space mapping based on synchrotron X-ray scattering to investigate the thermotropic phase behavior of dopamine-based ionic liquid crystals confined in cylindrical channels of 180 nm diameter in macroscopic anodic aluminum oxide membranes. As a function of the membranes’ hydrophilicity and thus the molecular anchoring to the pore walls (edge-on or face-on) and the variation of the hydrophilic-hydrophobic balance between the aromatic cores and the alkyl side chain motifs of the superdiscs by tailored chemical synthesis, we find a particularly rich phase behavior, which is not present in the bulk state. It is governed by a complex interplay of liquid crystalline elastic energies (bending and splay deformations), polar interactions, and pure geometric confinement and includes textural transitions between radial and axial alignment of the columns with respect to the long nanochannel axis. Furthermore, confinement-induced continuous order formation is observed in contrast to discontinuous first-order phase transitions, which can be quantitatively described by Landau-de Gennes free energy models for liquid crystalline order transitions in confinement. Our observations suggest that the infiltration of DILCs into nanoporous solids allows tailoring their nanoscale texture and ion channel formation and thus their electrical and optical functionalities over an even wider range than in the bulk state in a homogeneous manner on the centimeter scale as controlled by the monolithic nanoporous scaffolds.Publicationtype: Journal Article17 18 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Dynamic Kerr and Pockels electro-optics of liquid crystals in nanopores for active photonic metamaterials(Royal Society of Chemistry (RSC), 2021-11-05); ; ; ; Photonic metamaterials with properties unattainable in base materials are already beginning to revolutionize optical component design. However, their exceptional characteristics are often static, as artificially engineered into the material during the fabrication process. This limits their application for in-operando adjustable optical devices and active optics in general. Here, for a hybrid material consisting of a liquid crystal-infused nanoporous solid, we demonstrate active and dynamic control of its meta-optics by applying alternating electric fields parallel to the long axes of its cylindrical pores. First-harmonic Pockels and second-harmonic Kerr birefringence responses, strongly depending on the excitation frequency and temperature, are observed in a frequency range from 50 Hz to 50 kHz. This peculiar behavior is quantitatively traced by a Landau-De Gennes free energy analysis to an order-disorder orientational transition of the rod-like mesogens and intimately related changes in the molecular mobilities and polar anchoring at the solid walls on the single-pore, meta-atomic scale. Thus, our study provides evidence that liquid crystal-infused nanopores exhibit integrated multi-physical couplings and reversible phase changes that make them particularly promising for the design of photonic metamaterials with thermo-electrically tunable birefringence in the emerging field of space-time metamaterials aiming at full spatio-temporal control of light.Publicationtype: Journal Article70 392 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Anisotropic confinement of chromophores Induces second-order nonlinear optics in a nanoporous photonic metamaterial(Soc., 2021-02-15); ; ; ; Second-order nonlinear optics is the base for a large variety of devices aimed at the active manipulation of light. However, physical principles restrict its occurrence to non-centrosymmetric, anisotropic matter. This significantly limits the number of base materials exhibiting nonlinear optics. Here, we show that embedding chromophores in an array of conical channels 13 nm across in monolithic silica results in mesoscopic anisotropic matter and thus in a hybrid material showing second-harmonic generation (SHG). This non-linear optics is compared to the one achieved in corona-poled polymer films containing the identical chromophores. It originates in confinement-induced orientational order of the elongated guest molecules in the nanochannels. This leads to a non-centrosymmetric dipolar order and hence to a non-linear light-matter interaction on the sub-wavelength, single-pore scale. Our study demonstrates that the advent of large-scale, self-organised nanoporosity in monolithic solids along with confinement-controllable orientational order of chromophores at the single-pore scale provides a reliable and accessible tool to design materials with a nonlinear meta-optics.Publicationtype: Journal Article68 5 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Natural and chemically modified post-mining clays : structural and surface properties and preliminary tests on copper sorption(Multidisciplinary Digital Publishing Institute (MDPI), 2019-11-14); ; ; The structural and surface properties of natural and modified Pliocene clays from lignite mining are investigated in the paper. Chemical modifications are made using hydrofluoric acid (HF), sulfuric acid (H2SO4), hydrochloric acid (HCl), nitric acid (HNO3), sodium hydroxide (NaOH), and hydrogen peroxide (H2O2), at a concentration of 1 mol/dm3. Scanning electron microscopy is used to detect the morphology of the samples. Nitrogen adsorption isotherms were recorded to determine the specific surface area (SSA), mesoporosity, microporosity, and fractal dimensions. The raw clay has an SSA of 66 m2/g. The most promising changes in the structural properties are caused by modifications with HF or H2SO4 (e.g., the SSA increased by about 60%). In addition, the raw and modified clays are used in preliminary tests with Cu(II) sorption, which were performed in batch static method at initial Cu(II) concentrations of 25, 50, 80, 100, 200, 300, and 500 mg/dm3 in 1% aqueous suspensions of the clayey material. The maximum sorption of Cu(II) on the raw material was 15 mg/g. The structural changes after the modifications roughly reflect the capabilities of the adsorbents for Cu(II) adsorption. The modifications with HF and H2SO4 bring a similar improvement in Cu(II) adsorption, which is around 20–25% greater than for the raw material. The structural properties of investigated clays and their adsorptive capabilities indicate they could be used as low-cost adsorbents (e.g., for industrial water pretreatment).Publicationtype: Journal ArticleScopus© Citations 11 330 283 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Self-assembly of liquid crystals in nanoporous solids for adaptive photonic metamaterials(Royal Society of Chemistry (RSC), 2019); ; ; ; Nanoporous media exhibit structures significantly smaller than the wavelengths of visible light and can thus act as photonic metamaterials. Their optical functionality is not determined by the properties of the base materials, but rather by tailored, multiscale structures, in terms of precise pore shape, geometry, and orientation. Embedding liquid crystals in pore space provides additional opportunities to control light-matter interactions at the single-pore, meta-atomic scale. Here, we present temperature-dependent 3D reciprocal space mapping using synchrotron-based X-ray diffraction in combination with high-resolution birefringence experiments on disk-like mesogens (HAT6) imbibed in self-ordered arrays of parallel cylindrical pores 17 to 160nm across in monolithic anodic aluminium oxide (AAO). In agreement with Monte Carlo computer simulations we observe a remarkably rich self-assembly behaviour, unknown from the bulk state. It encompasses transitions between the isotropic liquid state and discotic stacking in linear columns as well as circular concentric ring formation perpendicular and parallel to the pore axis. These textural transitions underpin an optical birefringence functionality, tuneable in magnitude and in sign from positive to negative via pore size, pore surface-grafting and temperature. Our study demonstrates that the advent of large-scale, self-organised nanoporosity in monolithic solids along with confinement-controllable phase behaviour of liquid-crystalline matter at the single-pore scale provides a reliable and accessible tool to design materials with adjustable optical anisotropy, and thus offers versatile pathways to fine-tune polarisation-dependent light propagation speeds in materials. Such a tailorability is at the core of the emerging field of transformative optics, allowing, e.g., adjustable light absorbers and extremely thin metalenses.Publicationtype: Journal ArticleScopus© Citations 27 312 407