How does hybrid bridging core modification enhance the nonlinear optical properties in donor-π-acceptor configuration? A case study of dinitrophenol derivatives.

This study spotlights the fundamental insights about the structure and static first hyperpolarizability (ß) of a series of 2,4-dinitrophenol derivatives (1-5), which are designed by novel bridging core modifications. The central bridging core modifications show noteworthy effects to modulate the optical and nonlinear optical properties in these derivatives. The derivative systems show significantly large amplitudes of first hyperpolarizability as compared to parent system 1, which are 4, 46, 66, and 90% larger for systems 2, 3, 4, and 5, respectively, at Moller-Plesset (MP2)/6-31G* level of theory. The static first hyperpolarizability and frequency dependent coupled-perturbed Kohn-Sham first hyperpolarizability are calculated by means of MP2 and density functional theory methods and compared with respective experimental values wherever possible. Using two-level model with full-set of parameters dependence of transition energy (ΔΕ), transition dipole moment (µ(0)) as well as change in dipole moment from ground to excited state (Δµ), the origin of increase in ß amplitudes is traced from the change in dipole moment from ground to excited state. The causes of change in dipole moments are further discovered through sum of Mulliken atomic charges and intermolecular charge transfer spotted in frontier molecular orbitals analysis. Additionally, analysis of conformational isomers and UV-Visible spectra has been also performed for all designed derivatives. Thus, our present investigation provides novel and explanatory insights on the chemical nature and origin of intrinsic nonlinear optical (NLO) properties of 2,4-dinitrophenol derivatives.

Diradical character and nonlinear optical properties of buckyferrocenes: focusing on the use of suitably modified fullerene fragments.

The buckyferrocenes, synthesized through face-to-face fusion of ferrocene and fullerene fragments (C60Me10), are expected to enjoy the rich scientific heritage of ferrocene and fullerene with an extensively large π-conjugation network between the two Fe atoms [Y. Matsuo, K. Tahara and E. Nakamura, J. Am. Chem. Soc., 2006, 128, 7154]. However, the addition of pentamethyl groups at each end of the fullerene fragment breaks the π-conjugation path as well as metal-metal spin correlation between the two-ferrocene faces in a buckyferrocene. We found that the unblocking of π-conjugation from different positions in fullerene fragments have substantial effects on their topologies, spin densities, diradical characters as well as nonlinear optical (NLO) properties of these buckyferrocenes. We study the topological dependence of open-shell diradical character and second hyperpolarizability (γ), the third-order NLO properties at the molecular scale, in several buckyferrocenes. On the basis of their different diradical characters (yi), which are defined by the occupation number of the lowest unoccupied natural orbital (LUNO) + i (i = 0, 1,…), these buckyferrocenes are categorized into three groups, i.e., closed-shell (yi = 0), intermediate open-shell singlet (0 < yi < 1), and almost pure open-shell singlet (yi = 1) compounds. For example, we found that buckyferrocenes including (CpFe)2η(5)C60Me10 and (CpFe)2η(5)C70Me10 have closed-shell configurations. The buckyferrocenes (CpFe)2η(5)C60, (CpFe)2η(5)C70, (CpFe)2η(5)C70Me8, (CpFe)2η(5)C70Me4 and (CpFe)2η(5)C30 are intermediate open-shell singlet, while (CpFe)2η(5)C60Me4 and (CpFe)2η(5)C60Me8 are pure open-shell singlet complexes. Interestingly, the γzzzz amplitude of (CpFe)2η(5)C60, an open-shell intermediate diradical complex, is about 41 times and 13 times as large as those of its closed-shell ((CpFe)2η(5)C60Me10) and pure diradical ((CpFe)2η(5)C60Me8) counterparts, respectively. Similarly, the γzzzz amplitudes of (CpFe)2η(5)C70, (CpFe)2η(5)C70Me4, and (CpFe)2η(5)C70Me8 with intermediate diradical character are about 36, 17, and 9 times as large as that of their closed-shell (CpFe)2η(5)C70Me10 counterpart. The fact that larger γzzzz values are obtained for buckyferrocenes with intermediate diradical characters is in line with the "y-γ correlation" obtained from the valence configuration interaction (VCI) results for a two-site diradical model [M. Nakano, et al., Phys. Rev. Lett., 2007, 99, 033001] as well as for fullerene and graphene systems. The γzzzz density analysis shows that the large positive contributions originate from the large γzzzz density distributions on the upper- and lower-extended edges of the buckyferrocenes, between which significant spin polarizations appear within the spin-unrestricted DFT level of theory. These results demonstrate that such buckyferrocenes are potential candidates for a novel class of open-shell singlet NLO systems, where γzzzz values are modulated by tuning their diradical character through the use of suitably modified fullerene fragments.

Photodetection Enhancement via Graphene Oxide Deposition on Poly 3-Methyl Aniline.

A graphene oxide (GO)/poly 3-methyl aniline (P3MA) photodetector has been developed for light detection in a broad optical region: UV, Vis, and IR. The 3-methyl aniline was initially synthesized via radical polymerization using an acid medium, i.e., K2S2O8 oxidant. Consequently, the GO/P3MA composite was obtained through the adsorption of GO into the surface of P3MA. The chemical structure and optical properties of the prepared materials have been illustrated via XRD, FTIR, SEM, and TEM analysis. The absorbance measurements demonstrate good optical properties in the UV, Vis, and near-IR regions, although a decrease in the bandgap from 2.4 to 1.6 eV after the composite formation was located. The current density (Jph) varies between 0.29 and 0.68 mA·cm-2 (at 2.0 V) under dark and light, respectively. The photodetector has been tested using on/off chopped light at a low potential, in which the produced Jph values decrease from 0.14 to 0.04 µA·cm-2, respectively. The GO/P3MA photodetector exhibits excellent R (and D) values of 4 and 2.7 mA·W-1 (0.90 × 109 and 0.60 × 109 Jones) in the UV (340 nm) and IR (730 nm) regions, respectively. The R and D values obtained here make the prepared photodetector a promising candidate for future light detection instruments.

An analysis of the dye-sensitized solar cells fabricated with the dyes extracted from the leaves and flowers of Amaranthus cruentus.

Dye-sensitized solar cells (DSSCs) were devised with the sensitizers prepared from the leaves and flowers of Amaranthus cruentus. Fresh and dried leaves were employed for extracting the dye sensitizers. Acetone, ethanol, and deionized water were used as solvents for the extraction process. A sum of nine dyes was prepared. For all the extracted dyes, spectroscopic studies (UV-visible & FTIR) were performed to ensure that the dyes are suitable to be used as sensitizers for DSSC. XRD and SEM were recorded for the TiO2 paste used. Nine DSSCs were fabricated with the extracted dyes as sensitizers, TiO2 as semiconductor oxide, I-/I3- as electrolyte, and graphene-coated FTO as counter electrode. J-V characterization study was done for each cell showed that the cell with dye taken from the fresh leaves using acetone exhibited the highest efficiency of 0.816%. It was noted that these cells recorded higher efficiency than the previously reported works with dyes taken from Amaranthus red.

Enhanced Room Temperature Ammonia Gas Sensing Properties of Fe-Doped MoO3 Thin Films Fabricated Using Nebulizer Spray Pyrolysis.

MoO3 thin films are fabricated using nebulizer spray pyrolysis technique, which is doped with Fe at various concentrations of 1, 2, 3, and 4% for ammonia gas sensors application at room temperature. X-ray diffraction (XRD) study confirms the growth of the crystal by Fe doping up to 3%, nano rods shape morphology of the thin film samples observed by field emission scanning electron microscope (FESEM), reduction in bandgap is evidenced via UV-VIS spectrophotometer. Gas sensing study is performed using gas analyzing chamber attached with Keithley source meter. Since 3% Fe doped MoO3 sample displayed nano rods over the film surface which exhibits highest sensitivity of 38,500%, in a short period of raise and decay time 54 and 6 s. Our findings confirms that the 3% Fe doped MoO3 films suitability for ammonia gas sensing application.

Insights into the Impact of Yttrium Doping at the Ba and Ti Sites of BaTiO3 on the Electronic Structures and Optical Properties: A First-Principles Study.

We reported a systematic study of the effects of Y doping BaTiO3 at Ba and Ti sites. We assessed the structural, electronic, and optical properties by employing first-principles calculations within the Tran-Blaha-modified Becke-Johnson (TB-mBJ) potential and generalized gradient approximation + U approaches. We calculated the lattice constants and bond lengths for pure and Y-doped BaTiO3. We explored the consequences of electronic structure and optical property modification because of Y doping in BaTiO3. Indeed, Y doping has led to various modifications in the electronic structures of BaTiO3 by inducing a shift of the conduction band through lower energies for the Ba site and higher energies for the Ti site. It was found that Y doping, either at Ba or at Ti sites, strongly enhanced the BaTiO3 dielectric constant properties. The transformation in bonding was explored via the charge density contours and Born effective charges. We used the state of art of polarization theory based on finite difference and Berry-phase approaches to investigate piezoelectricity. Y doping has increased the dielectric constants but canceled the piezoelectricity as they changed to metallic nature. We could look into the future for potential doping, preserving the semiconductor nature of BaTiO3 and increasing the permittivity with large dielectric loss.