Structurally influenced optical nonlinearities and ultrafast dynamics in ß-acroleyl- and ß-dicyanobutadienyl-appended cobalt corroles.

The strong two-photon induced nonlinear absorption and self-focusing type positive nonlinear refraction are pronounced by the structural engineering in ß-functionalized cobalt corroles.

NaBiF4:Yb3+,Tm3+ submicron particles as luminescent probes for in vitro imaging of cells.

Upconversion materials have attracted considerable research interest for their application in bioimaging due to their unique optical properties. NaREF4 (RE = Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) based host lattice, which is widely used for upconversion, requires expensive rare-earth elements and tedious reaction conditions. Hence there is a need to develop environmentally friendly and cost effective materials for upconversion. In this study, we propose NaBiF4 as a host material for upconversion which is based on environmentally friendly and cost-effective bismuth. NaBiF4 has not been explored as an imaging probe before. We report efficient Yb3+/Tm3+ doped NaBiF4 based upconversion submicron particles which exhibit a photostable, wide upconversion emission range (NIR-to-NIR and Vis) under NIR (980 nm) excitation, and in-vitro non-cytotoxic uptake by mammalian cancer cell lines as well as bacterial cells with a high signal to background ratio. The synthesis of the chosen host material co-doped with Yb3+/Tm3+ has not been reported earlier through such a non-aqueous quaternary reverse micelle route. Here, we functionally validate these submicron particles as viable alternatives to currently available upconversion nanomaterials and highlight their potential as luminescent probes for bioimaging.

Ultrafast Dynamics and Strong Two-Photon Absorption Properties of Nonplanar ß-Functionalized "Push-Pull" Copper Corroles with a Mixed Substituent Pattern.

A new series of nonplanar and unsymmetrically ß-functionalized "push-pull" copper corroles, CuTPC(CHO)R7 [R = H, Br, Ph, Me, or 2-thienyl (Th)], were synthesized and characterized to elucidate the effect of ß-functionalization and nonplanarity on the photophysical, redox, and nonlinear optical (NLO) properties on the corrole ring. The synthetic route to unsymmetrically ß-octasubstituted copper corroles includes bromination of CuTPC(CHO) to get CuTPC(CHO)Br7 in 80% yield, which was further subjected to the Pd-catalyzed Suzuki reaction. CuTPC(CHO)Br7 exhibited a large red shift in the Soret band (Δλmax = 35-40 nm) and both the Q bands (Δλmax = 10-50 nm), as compared to CuTPC and CuTPC(CHO). CuTPC(CHO)Br7 was 510 and 290 mV anodically shifted in the first oxidation and the first reduction compared to CuTPC owing to the strong -I effect of CHO and Br groups. Density functional theory studies revealed that all the ß-octasubstituted copper corroles exhibited highly nonplanar saddle-shape conformation of the corrole ring. Very high torsional saddling was observed for CuTPC(CHO)Th7 (79-83°) than that for CuTPC (49-53°), even larger than that for CuTPCBr8 (67-70°). Femtosecond laser-induced third-order NLO studies from these copper corroles showed strong two-photon absorption cross-sections (0.48-6.98 × 104 GM) and self-focusing-type positive nonlinear refraction behavior. The observed structure-dependent two-photon absorption coefficients (ß) are in the range of ∼2.7-20.9 × 10-12 m/W, and the n2 values are in the range of ∼0.64-6.45 × 10-18 m2/W. The present results may facilitate a new window for these copper corroles in nonlinear optical devices, femtosecond optical limiters, and many other ultrafast photonic applications.

ß-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters.

A series of ß-TCBD (1,1,4,4-tetracyano-buta-1,3-diene)-appended porphyrins, M-TCBD (M = 2H, Co(II), Ni(II), Cu(II), and Zn(II)), was synthesized from 2,3-diphenylethynyl-12-nitro-meso-tetraphenylporphyrin, H2-PE2, and characterized by various spectroscopic techniques and electrochemical studies. The reaction proceeds via [2 + 2] cycloaddition and retroelectrocyclization reactions of tetracyanoethylene (TCNE) with H2-PE2. The observed unusual reduction potentials in the cyclic voltammograms of the synthesized porphyrins in the range of -0.06 to -0.10 V are the consequence of the TCBD moiety present at the ß-position of the porphyrin macrocycle. Notably, these porphyrins exhibited three porphyrin ring-centered reductions due to extended π-conjugation. The higher nonlinear optical response exhibited by the M-TCBD series as compared to the precursor (H2-PE2) was attributed to the existence of intramolecular charge transfer and enhanced polarization in the M-TCBD series. The single-beam femtosecond Z-scan measurements were performed to elucidate the third-order nonlinear optical properties, and the temporal response of these porphyrin molecules was investigated using optical pump-probe spectroscopy to study the excited state absorption dynamics. Z-scan measurements revealed that Co-TCBD exhibited a higher nonlinear optical response as compared to free base porphyrins. The two-photon absorption coefficient (ß) and the imaginary part of third-order nonlinear optical susceptibility (χ(3)) were obtained from the open aperture experiment, whereas the close aperture experiment delivered the magnitude and the sign of the nonlinear refractive index (n2) and the real part of χ(3). Furthermore, the femtosecond transient absorption spectroscopy revealed a faster relaxation dynamics of various absorption processes in a picosecond timescale. The excellent optical limiting threshold (1.90-2.33 × 1015 W/m2) of the synthesized porphyrins makes them good materials for laser protection and high-power laser operation.

KLa(0.95-x)GdxF4:Eu3+ hexagonal phase nanoparticles as luminescent probes for in vitro Huh-7 cancer cell imaging.

A facile chemical route is reported for synthesizing red-emitting photoluminescent/MRI multi-functional KLa(0.95-x)GdxF4:Eu3+ (x = 0 to 0.4) bio-compatible nanomaterials for targeted in vitro tumor imaging. Hexagonal phase pure nanoparticles show a significant and systematic change in morphology with enhanced photoluminescence due to the substitution of La3+ with Gd3+ ions. Single phase ß-KLa(0.95-x)GdxF4:Eu3+ exhibits multifunctional properties, both intense red emission and strong paramagnetism for high-contrast bioimaging applications. These silica capped magnetic/luminescent nanoparticles show long-term colloidal stability, optical transparency in water, strong red emission, and low cytotoxicity. The cellular uptake of coated nanoparticles was investigated in liver cancer cell line Huh-7. Our findings suggest that these nanoparticles can serve as highly luminescent imaging probes for in vitro applications with potential for in vivo and live cell imaging applications.

Synthesis, Structural, Linear, and Nonlinear Optical Studies of Inorganic-Organic Hybrid Semiconductors (R-C6H4CHCH3NH3)2PbI4, (R = CH3, Cl).

Synthesis, crystal structure, and optical properties of two-dimensional (2D) layered structurally slightly different inorganic-organic (IO) hybrid semiconductors (R-C6H4C2H4NH3)2PbI4 (R = CH3, Cl) are presented. They are naturally self-assembled systems where two (RNH3)+ moieties are sandwiched between two infinitely extended 2D layers of the [PbI6]4- octahedral network and treated as natural IO multiple quantum wells. While the former compound crystallizes into an orthorhombic system in the Cmc21 space group, the latter crystallizes into a monoclinic system in the space group P21/c. As a thin film, they are well-oriented along the (l00) direction. Both single crystals and thin films show strong room-temperature Mott type exciton features that are highly sensitive to the self-assembly and crystal packing. Linear (one-photon) and nonlinear (two-photon) optical probing of single crystals for exciton photoluminescence imaging and spectral spatial mapping provide deep insight into the layered re-arrangement and structural crumpling due to organic conformation. The strongly confined excitons, within the lowest band gap of inorganic, show distinctly different one- and two-photon excited photoluminescence peaks: free excitons from perfectly aligned 2D self-assembly and energy down-shifted excitons originated from the locally crumpled layered arrangement. Their structural aspects are successfully presented with proper correlation that emphasize various differences in physical and optical properties associated between these novel IO hybrids.

Strong Photocurrent from Two-Dimensional Excitons in Solution-Processed Stacked Perovskite Semiconductor Sheets.

Room-temperature photocurrent measurements in two-dimensional (2D) inorganic-organic perovskite devices reveal that excitons strongly contribute to the photocurrents despite possessing binding energies over 10 times larger than the thermal energies. The p-type (C6H9C2H4NH3)2PbI4 liberates photocarriers at metallic Schottky aluminum contacts, but incorporating electron- and hole-transport layers enhances the extracted photocurrents by 100-fold. A further 10-fold gain is found when TiO2 nanoparticles are directly integrated into the perovskite layers, although the 2D exciton semiconducting layers are not significantly disrupted. These results show that strong excitonic materials may be useful as photovoltaic materials despite high exciton binding energies and suggest mechanisms to better understand the photovoltaic properties of the related three-dimensional perovskites.

Novel fluorite structured superparamagnetic RbGdF4 nanocrystals as versatile upconversion host.

Fluorite structured nanocrystals of RbGdF4 in cubic symmetry have successfully been synthesized by employing a simple, one-step, and template-free wet chemical method at room temperature. Considering the structural model of cubic KLaF4 in the Fm̅3m space group, the observed powder X-ray diffraction (PXRD) pattern was fitted by the Le Bail procedure with the cubic lattice constant of a = 5.8244 (1) Å. Both high-resolution transmission electron microscopic (HR-TEM) and dynamic light scattering (DLS) measurements revealed the monodispersity of the nanocrystals with their size in the range of 2-18 nm. Upon excitation at 980 nm, Yb(3+), (Er(3+)/Ho(3+)/Tm(3+)) codoped RbGdF4 nanocrystals showed multicolor upconversion including red, yellow, blue, and the combination of basic color (near-white) emissions. Also, near-white upconversion emission from Yb(3+), Ho(3+), Tm(3+) triply doped cubic RbGdF4 nanocrystals was observed at varying laser power densities. RbGdF4 nanocrystals exhibited superparamagnetic behavior with a molar magnetic susceptibility of 2.61 × 10(-2) emu·Oe(-1)·mol(-1) at room temperature, while at low temperature (5 K) a saturation magnetization value of 90.41 emu·g(-1) at an applied field of at 10 kOe was observed. Non-interaction of the localized magnetic moment of Gd(3+) ions in the host matrix has been reasoned out for the observed superparamagnetic behavior. From the Langevin fit of the magnetic data, the average particle diameter obtained was approximately 2.2 nm, matching well with the values from other measurements. RbGdF4 nanocrystals exhibited a large ionic longitudinal relaxivity (r1 = 2.30 s(-1)·mM(-1)), suggesting their potential applicability as a promising agent for T1 contrast magnetic resonance imaging (MRI) in addition to the applications arising from the coupling of optical and magnetic functions such as multiplexing biodetection, bioimaging (optical and MRI), and other optical technologies.

Hexagonally ordered KLaF4 host: phase-controlled synthesis and luminescence studies.

Experiments resulting in the successful synthesis of hexagonally ordered KLaF(4) have been described for the first time. Syntheses from three different lanthanum precursors and KF under nonaqueous conditions and at atmospheric pressure are presented. The temperature, time of the fluorination reactions, and lanthanum precursor influenced the formation of hexagonal KLaF(4). While La(O(i)Pr)(3) and La(acac)(3) yielded hexagonal KLaF(4) by their reaction with KF in methanol at 65 °C, LaCl(3) favored only the formation of cubic KLaF(4) at 25 °C (room temperature). Size-induced phase transformation from cubic KLaF(4) to its hexagonal polymorph has been proposed for the reactions involving La(acac)(3) and La(O(i)Pr)(3) and KF. Rietveld refinement of the powder X-ray diffraction pattern of the hexagonally ordered KLaF(4) was successfully carried out in space group P6̅2m (No. 189) with lattice constants a = 6.5842(3) Å and c = 3.8165(3) Ǻ. A relatively lower effective phonon energy of 262 cm(-1) observed for the hexagonally ordered KLaF(4) (determined from its Raman spectrum) suggests its potential as a host for optically active elements with the possibility of minimized nonradiative processes. The hexagonal KLaF(4) sample was doped with Er(3+) ion (3 mol %) and systematically investigated by diffuse reflectance, normal emission, and upconversion studies. Strong green emission ((4)S(3/2), (2)H(11/2) → (4)I(15/2)) has been observed upon 980 and 460 nm excitation. A highly transparent light-emitting polymer [poly(methyl methacrylate)] composite containing hexagonal KLaF(4):Er(3+) phosphor has also been effectively demonstrated for many potential applications.

Strong-coupling in inorganic-organic hybrid embedded single and coupled metallic microcavities.

Here we fabricated and studied highly-layered Inorganic-Organic Multiple Quantum Well structures and later placed them into metallic low quality factor microcavities. Room-temperature strong exciton-photon coupling is achieved in such single and coupled microcavities. Upon angle tuning, the broad photonic mode of the microcavities is clearly split into two modes at the exciton resonant absorption of hybrid perovskite. The large Rabi splitting upto -213 meV is obtained in good agreement with the theoretical models.

Optical and structural features of silicon-rich hydrogenated amorphous silicon nitride thin films.

A systematic study of fabrication and effect of post-deposition processing on the optical and structural features of silicon-rich hydrogenated amorphous silicon nitride thin films deposited by Hg-sensitized Photo-Chemical Vapour Deposition technique is presented. Both deposition parameters and post-deposition thermal treatment resulted into substantial change in the refractive index associated with the densification of the film. Our studies reveal that the presence of hydrogen and its out-diffusion upon thermal treatment play a crucial role in the overall structural evolution, specially the stabilization of individual phases such as Si and Si3N4. We further report the room-temperature photoluminescence from as-deposited films, which is due to formation of silicon nanostructures in crystalline and amorphous forms. These studies are of great interest from the prospective of commercially viable Si-based technology.

Anisotropic behavior of water in ferroelectric liquid crystals.

The outcome of water addition in ferroelectric liquid crystal (FLC) has been investigated in uniform and defect-free homogeneous and homeotropically aligned monodomain sample cells from electro-optical and dielectric spectroscopic measurements. The lagging in optical response between nonconducting (spatially variable switching) and conducting (conventional switching) portions of water added FLC sample cell has been observed by frequency-dependent electro-optical studies. The bias-dependent water related new relaxation peak near the conventional Goldstone mode relaxation process has been observed only in the homogeneous alignment and not in the homeotropic one. Further, the significant increment in dielectric anisotropy as well as faster diffusion of water along long molecular axis than short molecular axis has also been monitored. These studies strongly suggest that the distribution of water is anisotropic in FLC medium and could be the reason for new relaxation peak in the water added FLC sample.

Strong exciton-photon coupling in inorganic-organic multiple quantum wells embedded low-Q microcavity.

Optoelectronic-compatible heterostructures are fabricated from layered inorganic-organic multiple quantum wells (IO-MQW) of Cyclohexenyl ethyl ammonium lead iodide, (C(6)H(9)C(2)H(4)NH(3))(2)PbI(4) (CHPI). These hybrids possess strongly-resonant optical features, are thermally stable and compatible with hybrid photonics assembly. Room-temperature strong-coupling is observed when these hybrids are straightforwardly embedded in metal-air (M-A) and metal-metal (M-M) low-Q microcavities, due to the large oscillator strength of these IO-MQWs. The strength of the Rabi splitting is 130 meV for M-A and 160 meV for M-M cavities. These values are significantly higher than for J-aggregates in all-metal microcavities of similar length. These experimental results are in good agreement with transfer matrix simulations based on resonant excitons. Incorporating exciton-switching hybrids allows active control of the strong-coupling parameters by temperature, suggesting new device applications.

Control of topological defects in microstructured liquid crystal cells.

We study how the propagation of light inside recently developed micro-structured cells, can be actively tuned by polarising the nanoscale defects in the nematic liquid crystals they contain. Our 'planar-spherical' cells are formed by assembling a planar and a gold-coated hemispherical micro-mirror. Optical reflection images of the back-reflected polarised light show a remarkable change of symmetry as a function of the voltage applied to the cell. Theoretical models of the alignment of the liquid crystal within the cell indicate that the constraints imposed on the liquid crystal by the cell geometry and by the applied electric field induces the formation of defects. Their motion under the effect of the applied electric field is responsible for the change of symmetry of the back-reflected light. Furthermore, experimental measurements of the relaxation time of the back-reflected intensity indicate that the motion of the defect in our micro-structured cells is much faster than in equivalent planar cells.