Stereoselective synthesis of unnatural α-amino acid derivatives through photoredox catalysis.

A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural α-amino acids. The developed protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. The protocol utilizes near-stoichiometric amounts of the imine and the acid radical precursor in combination with a catalytic amount of an organic acridinium-based photocatalyst. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.

Synthetic Control on Structure/Dimensionality and Photophysical Properties of Low Dimensional Organic Lead Bromide Perovskite.

Low dimensional lead halide perovskites have attracted huge research interest due to their structural diversity and remarkable photophysical properties. The ability to controllably change dimensionality/structure of perovskites remains highly challenging. Here, we report synthetic control on structure/dimensionality of ethylenediammonium (ED) lead bromide perovskite from a two dimensionally networked (2DN) sheet to a one dimensionally networked (1DN) chain structure. Intercalation of solvent molecules into the perovskite plays a crucial role in directing the final dimensionality/structure. This change in dimensionality reflects strongly in the observed differences in photophysical properties. Upon UV excitation, the 1DN structure emits white light due to easily formed " self-trapped" excitons. 2DN perovskites show band edge blue emission (∼410 nm). Interestingly, Mn2+ incorporated 2DN perovskites show a highly red-shifted Mn2+ emission peak at ∼670 nm. Such a long wavelength Mn2+ emission peak is unprecedented in the perovskite family. This report highlights the synthetic ability to control the dimensionality/structure of perovskite and consequently its photophysical properties.

Energy Transfer Mechanisms and Optical Thermometry of BaMgF4:Yb3+,Er3+ Phosphor.

Motivated from our previous studies on the upconversion properties of BaMgF4:Yb3+,Tb3+ phosphor, here we investigated the upconversion properties of BaMgF4:Yb3+,Er3+ phosphor. We demonstrate a two-way versatile approach for the fine-tuning of emission from green to the red region, by varying the dopant concentration and adjusting the pulse width of an infrared laser. The mechanism involved in tuning the emission color by laser power and pulse width variation was illustrated in detail. The temperature dependent upconversion spectra were studied by analyzing the fluorescence intensity ratio of the thermally coupled levels. The maximum sensitivity obtained is 83.29 × 10-4 K-1 at 583 K, which is much higher than the temperature sensitivity reported for other fluoride based materials. Moreover, the influence of the excitation power density on the ability of the phosphor for temperature sensing was also investigated. We obtained a maximum (∼415 K) temperature detection at 2563 mW laser power. The obtained results illustrate the potential use of BaMgF4:Yb3+,Er3+ phosphor in an optical thermometer due to its highly sensitive temperature detection ability.

Behavior of Methylammonium Dipoles in MAPbX3 (X = Br and I).

Dielectric constants of MAPbX3 (X = Br, I) in the 1 kHz-1 MHz range show strong temperature dependence near room temperature, in contrast to the nearly temperature-independent dielectric constant of CsPbBr3. This strong temperature dependence for MAPbX3 in the tetragonal phase is attributed to the MA+ dipoles rotating freely within the probing time scale. This interpretation is supported by ab initio molecular dynamics simulations on MAPbI3 that establish these dipoles as randomly oriented with a rotational relaxation time scale of ∼7 ps at 300 K. Further, we probe the intriguing possibility of transient polarization of these dipoles following a photoexcitation process with important consequences on the photovoltaic efficiency, using a photoexcitation pump and second harmonic generation efficiency as a probe with delay times spanning 100 fs-1.8 ns. The absence of a second harmonic signal at any delay time rules out the possibility of any transient ferroelectric state under photoexcitation.

Spectroscopic Investigation of Up-Conversion Properties in Green Emitting BaMgF4:Yb3+,Tb3+ Phosphor.

In this work we have comprehensively studied the up-conversion (UC) properties of BaMgF4:Yb3+,Tb3+ phosphor for the first time. BaMgF4:Yb3+,Tb3+ phosphors were prepared by a simple and low cost precipitation method. To determine the influence of dopant concentration on luminescence properties, the corresponding UC luminescence spectra of BaMgF4:Yb3+,Tb3+ phosphors were studied under NIR excitation. Emission spectra under NIR excitation reveal the vital role of Tb3+ concentration in spectral tuning from the blue to green region. The UC decay curves were also studied to explore the possible energy transfer (ET) mechanisms between Yb3+ and Tb3+. The results reported here are expected to provide an approach for better understanding ET mechanisms in many Yb3+/Tb3+ codoped UC phosphors. This study will be helpful in applications where precisely defined optical transitions is an essential criterion.

Luminescence characterization of Dy and Eu doped Na6 Mg(SO4 )4 phosphors.

A series of single-phase phosphors based on Na6 Mg(SO4 )4 (Zeff  = 11.70) doped with Dy and Eu was prepared by the wet chemical method. The photoluminescence (PL) and thermoluminescence (TL) properties of Dy3+ - and Eu3+ -activated Na6 Mg(SO4 )4 phosphors were investigated. The characteristic emissions of Dy3+ and Eu3+ were observed in the Na6 Mg(SO4 )4 host. The TL glow curve of the Na6 Mg(SO4 )4 :Dy phosphor consisted of a prominent peak at 234°C and a very small hump at 158°C. The TL sensitivity of the Na6 Mg(SO4 )4 :Dy phosphor was found to be four times less than the commercialized CaSO4 :Dy phosphor. The TL dose-response of the Na6 Mg(SO4 )4 :Dy phosphor was studied from a dose range of 5-10 kGy and the linear dose-response was observed up to 1 kGy which is good for a microcrystalline phosphor. Trapping parameters for both the samples were calculated using the Initial Rise and Chen's peak shape methods.

Is CH3NH3PbI3 Polar?

In view of the continued controversy concerning the polar/nonpolar nature of the hybrid perovskite system, CH3NH3PbI3, we report the first investigation of a time-resolved pump-probe measurement of the second harmonic generation efficiency as well as using its more traditional form as a sensitive probe of the absence/presence of the center of inversion in the system both in its excited and ground states, respectively. Our results clearly show that SHG efficiency, if nonzero, is below the limit of detection, strongly indicative of a nonpolar or centrosymmetric structure. Our results on the same samples, based on temperature dependent single crystal X-ray diffraction and P-E loop measurements, are entirely consistent with the above conclusion of a centrosymmetric structure for this compound in all three phases, namely the high temperature cubic phase, the intermediate temperature tetragonal phase and the low temperature orthorhombic phase. It is important to note that all our experimental probes are volume averaging and performed on bulk materials, suggesting that basic material properties of CH3NH3PbI3 are consistent with a centrosymmetric, nonpolar structure.

Systematic study of photoluminescence, lyoluminescence and mechanoluminescence in Ce3+ - and Eu3+ -activated Li3 PO4 phosphors.

Li3 PO4 phosphor was prepared using a modified solid-state diffusion technique. In this work, photoluminescence, lyoluminescence and mechanoluminescence studies were carried out in a Li3 PO4 microcrystalline powder doped with different rare earths. In photoluminescence studies, characteristic emission of Ce and Eu was observed. The lyoluminescence glow curves of Li3 PO4 microcrystals show that lyoluminescence intensity initially increases with time and then decreases exponentially. The decay time consists of two components for all masses. The dependence of decay time, especially the longer component, on mass has been investigated. Experiments on γ-irradiated crystals have proved that the light emission originates from the recombination of released F-centres with trapped holes (V2-centres) at the sulfuric acid-solid interface. Incorporation of bivalent alkali in solid lithium phosphate leads to an enhancement of lyoluminescence. A possible explanation for the experimental results has been attempted. The phosphor has a mechanoluminescence single glow peak. Mechanoluminescence intensity under various loading conditions was investigated. It is observed that mechanoluminescence intensity increases with increasing impurity concentration and increasing piston impact velocity. The results may be considered as only being of academic interest in solid-state materials.