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Water-stable, lead-free zero-dimensional (0D) organic–inorganic hybrid colloidal tin(IV) perovskite, A2SnX6 (A is a monocationic organic ion and X is a halide) nanocrystals (NCs) with high photoluminescence (PL) quantum yield (QY) have rarely been explored. Herein, we report solution-processed colloidal NCs of blue light-emitting T2SnCl6 and orange light-emitting T2Sn1-xSbxCl6 [T+ = tetramethylammonium cation] from their corresponding single crystals (SCs). These colloidal NCs are well-dispersible in non-polar solvents, thereby maintaining their bright emission. This paves the way for fabricating homogeneous thin films of these NCs. Due to organic cation (T+)-controlled large spin–orbit coupling (SOC), the T2Sn1-xSbxCl6 NCs exhibit bright orange emission with an enhancement in PL QY of 41% compared to their bulk counterpart. Furthermore, we explore T2Sn1-xBixCl6 and T2Sn1-x-yBixSbyCl6 SCs, which show blue and green emission, respectively; the latter is attributed to the newly formed Sb 5p and Sb 5 s orbital-driven band structures confirmed by applying density functional theory (DFT) calculations. The SCs and NCs exhibit excellent stability in water under ambient conditions because of the in-situ generation of a hydrophobic and oxygen-resistant passivating layer of oxychloride in the presence of water. Our findings open a pathway for designing lead-free perovskites materials for thin-film-based optoelectronic devices.

Lead-free, non-toxic transition metal-based phosphorescent organic–inorganic hybrid (OIH) compounds are promising for next-generation flat-panel displays and solid-state light-emitting devices. In the present study, we fabricate highly efficient phosphorescent green-light-emitting diodes (PHOLEDs) using the lead-free, non-toxic, zero-dimensional OIH compound [(H2CCHCH2)(C6H5)3P]2MnBr4 (1), which exhibits an emission peak at 516 nm and a long lifetime of 441 μs. The long lifetime indicates the phosphorescent emissive nature of 1. Density functional theory calculations confirm that the narrow green emission from 1 is due to the highly localized electronic states of the valence and conduction bands. A flexible green-light-emitting phosphorescent substrate is successfully fabricated from 1 using a nylon membrane, indicating that 1 has a significant potential for use in flexible optoelectronic devices. By engineering the organic hole and electron transport layers, we achieve a highly efficient all-vacuum-deposited PHOLED with a current efficiency of 24.71 cd A−1, a power efficiency of 20.61 lm W−1, and an external quantum efficiency of 7.12%. Together, our findings will pave the way for the development of high-performance Mn(II)-based LEDs.

We report, for the first time, the solid-phase gram-scale synthesis of two lead-free, zero-dimensional (0D) fluorescent organic–inorganic hybrid compounds, [Bu4N]2[MnBr4] (1) and [Ph4P]2[MnBr4] (2), achieved by grinding the organic and inorganic precursor salts. The solid-phase synthetic route has several advantages for modulating molecular dimensionalities. During grinding, organic cations and Mn2+ cations are co-crystallized together in the solid-state, forming a 0D assembly at the molecular level where each individual metal center is surrounded by organic cations. Both compounds exhibit an emission peak at 520 nm and a photoluminescence (PL) quantum yield (QY) of 47%. Here, we also report, for the first time, the upconversion phenomena which trigger different emission energies occurring in different quartet states of Mn, 4T1(4G), 4T2(4G), 4A1(4G), 4E(4G), 4T2(4D), 4E(4D), and 4T1(4P). These optical properties are unusual phenomena which break Kasha's rule of emission. Single particle imaging and low-temperature PL measurement are performed to obtain a deeper insight into these ground products. These results pave a new path to develop highly fluorescent non-toxic hybrid compounds with remarkable optical properties.

There has been no report on the synthesis of fluorescent α-phase stabilized quasi-2D FAPbI3 [FA = CH(NH2)2] perovskite nanocrystals (NCs) in water. We report the top–down synthesis of fluorescent quasi-two dimensional (2D) α-FAPbI3 NCs in aqueous media by controlling the electronic states of lead and the NCs size of FAPbI3. The product was stable in ambient conditions for more than six months. We explored a detailed synthetic study, their emissive properties and phase stabilization mechanism corroborated by density functional theory (DFT) calculations. Single particle imaging and photoluminescence (PL) study of α-FAPbI3 NCs bear the signature of dual emission, which indicates the formation of self-trapped excited states. Our findings will pave the way to develop phase-stabilized hybrid perovskite NCs in water, beneficial for optoelectronic devices.

Water-stable, lead-free zero-dimensional (0D) organic-inorganic hybrid colloidal tin(IV) perovskite, A

Rotaxane-based molecular shuttles are often operated using low-symmetry axles and changing the states of the binding stations. A molecular shuttle capable of directional shuttling of an acid-responsive cone-like macrocycle on a single-state symmetric dumbbell axle is now presented. The axle contains three binding stations: one symmetric di(quaternary ammonium) station and two nonsymmetric phenyl triazole stations arranged in opposite orientations. Upon addition of an acid, the protonated macrocycle shuttles from the di(quaternary ammonium) station to the phenyl triazole binding station closer to its butyl groups. This directional shuttling presumably originates from charge repulsion and an orientational binding preference between the cone-like cavity and the nonsymmetric phenyl triazole station. This mechanism for achieving directional shuttling by manipulating only the wheels instead of the tracks is new for artificial molecular machines.

A series of Zn–porphyrin dyes was prepared and anchored onto a TiO2 surface to complete a dye-sensitized photocatalyst system, Zn–porphyrin-|TiO2|-Cat, and tested as lower energy photosensitizers for photocatalytic CO2 reduction. Three major synthetic modifications were performed on the Zn–porphyrin dye to obtain a lower energy sensitization and improve the catalyst lifetime. We found that incorporating acetylene and linear hexyl groups into the Zn–porphyrin core allowed facile lower energy sensitization, and the addition of the cyanophosphonic acid as an anchoring group gave the long-term dye stability on the TiO2 surface. Under irradiation with red light of >550 nm and a light intensity of 207 mW/cm2, the hybrid ZnPCNPA catalyst showed a TONRe of ∼800 over an extended time period of 90 h. The photocatalytic activities of porphyrin hybrids differ greatly with the binding strength of the anchoring groups of dye and spectral range of the irradiated light and its intensity.

White organic light-emitting diode (WOLED) technology has attracted considerable attention because of its potential use as a next-generation solid-state lighting source. However, most of the reported WOLEDs that employ the combination of multi-emissive materials to generate white emission may suffer from color instability, high material cost, and a complex fabrication procedure which can be diminished by the single-emitter-based WOLED. Herein, a color-tunable material, tris(4-(phenylethynyl)phenyl)amine (TPEPA), is reported, whose photoluminescence (PL) spectrum is altered by adjusting the thermal annealing temperature nearly encompassing the entire visible spectra. Density functional theory calculations and transmission electron microscopy results offer mechanistic understanding of the PL redshift resulting from thermally activated rotation of benzene rings and rotation of 4-(phenylethynyl) phenyl)amine connected to the central nitrogen atom that lead to formation of ordered molecular packing which improves the π-π stacking degree and increases electronic coupling. Further, by precisely controlling the annealing time and temperature, a white-light OLED is fabricated with the maximum external quantum efficiency of 3.4% with TPEPA as the only emissive molecule. As far as it is known, thus far, this is the best performance achieved for single small organic molecule based WOLED devices.