Solution-processable mixed-anion cluster chalcohalide Rb6Re6S8I8 in a light-emitting diode.

Rhenium chalcohalide cluster compounds are a photoluminescent family of mixed-anion chalcohalide cluster materials. Here we report the new material Rb6Re6S8I8, which crystallizes in the cubic space group Fm[Formula: see text]m and contains isolated [Re6S8I6]4- clusters. Rb6Re6S8I8 has a band gap of 2.06(5) eV and an ionization energy of 5.51(3) eV, and exhibits broad photoluminescence (PL) ranging from 1.01 eV to 2.12 eV. The room-temperature PL exhibits a PL quantum yield of 42.7% and a PL lifetime of 77 µs (99 µs at 77 K). Rb6Re6S8I8 is found to be soluble in multiple polar solvents including N,N-dimethylformamide, which enables solution processing of the material into films with thickness under 150 nm. Light-emitting diodes based on films of Rb6Re6S8I8 were fabricated, demonstrating the potential for this family of materials in optoelectronic devices.

Nonequilibrium Lattice Dynamics in Photoexcited 2D Perovskites.

Interplay between structural and photophysical properties of metal halide perovskites is critical to their utility in optoelectronics, but there is limited understanding of lattice response upon photoexcitation. Here, 2D perovskites butylammonium lead iodide, (BA)2 PbI4 , and phenethylammonium lead iodide, (PEA)2 PbI4 , are investigated using ultrafast transient X-ray diffraction as a function of optical excitation fluence to discern structural dynamics. Both powder X-ray diffraction and time-resolved photoluminescence linewidths narrow over 1 ns following optical excitation for the fluence range studied, concurrent with slight redshifting of the optical bandgaps. These observations are attributed to transient relaxation and ordering of distorted lead iodide octahedra stimulated mainly by electron-hole pair creation. The c axis expands up to 0.37% over hundreds of picoseconds; reflections sampling the a and b axes undergo one tenth of this expansion with the same timescale. Post-photoexcitation appearance of the (110) reflection in (BA)2 PbI4 would suggest a transient phase transition, however, through new single-crystal XRD, reflections are found that violate glide plane conditions in the reported Pbca structure. The static structure space group is reassigned as P21 21 21 . With this, a nonequilibrium phase transition is ruled out. These findings offer increased understanding of remarkable lattice response in 2D perovskites upon excitation.

AInSn2S6 (A = K, Rb, Cs)─Layered Semiconductors Based on the SnS2 Structure.

RbInSn2S6 and CsInSn2S6 are yellow two-dimensional (2D) semiconductors featuring anionic SnS2-type layers of edge-sharing (In/Sn)S6 octahedra. These structures are directly derived from the parent structure of SnS2 by replacement of Sn4+ atoms with A+ and In3+ atoms. The compounds crystallize, isotypic to the ion-exchange material KInSn2S6. They adopt the triclinic space group R3̅m (no. 166). The compounds have similar indirect optical band gaps of 2.31(5) eV for Rb and 2.47(5) eV Cs. The measured work functions for each material are ∼5.38 eV. The density functional theory-calculated effective mass values exhibit strong anisotropy due to the 2D nature of the crystal structures and in the case of CsInSn2S6 for hole carriers along the a, b, and c crystallographic directions are 0.30 m0, 0.34 m0, and 2.54 m0, respectively, while for electrons are 0.06 m0, 0.07 m0, and 0.47 m0, respectively.

Cubic Stuffed-Diamond Semiconductors LiCu3TiQ4 (Q = S, Se, and Te).

Lithium chalcogenides have been understudied, owing to the difficulty in managing the chemical reactivity of lithium. These materials are of interest as potential ion conductors and thermal neutron detectors. In this study, we describe three new cubic lithium copper chalcotitanates that crystallize in the P4̅3m space group. LiCu3TiS4, a = 5.5064(6) Å, and LiCu3TiSe4, a = 5.7122(7) Å, represent two members of a new stuffed diamond-type crystal structure, while LiCu3TiTe4, a = 5.9830(7) Å crystallized into a similar structure exhibiting lithium and copper mixed occupancy. These structures can be understood as hybrids of the zinc-blende and sulvanite structure types. In situ powder X-ray diffraction was utilized to construct a "panoramic" reaction map for the preparation of LiCu3TiTe4, facilitating the design of a rational synthesis and uncovering three new transient phases. LiCu3TiS4 and LiCu3TiSe4 are thermally stable up to 1000 °C under vacuum, while LiCu3TiTe4 partially decomposes when slowly cooled to 400 °C. Density functional theory calculations suggest that these compounds are indirect band gap semiconductors. The measured work functions are 4.77(5), 4.56(5), and 4.69(5) eV, and the measured band gaps are 2.23(5), 1.86(5), and 1.34(5) eV for the S, Se, and Te analogues, respectively.

Mixed Anion Semiconductor In8S2.82Te6.18(Te2)3.

The new heteroanionic compound In8S2.82Te6.18(Te2)3 crystallizes in the monoclinic space group C2/c with lattice parameters a = 14.2940(6) Å, b = 14.3092(4) Å, c = 14.1552(6) Å, and ß = 90.845(3)°. The three-dimensional (3D) framework of In8S2.82Te6.18(Te2)3 is composed of a complex 3D network of corner-connected InQ4 tetrahedra with three Te22- dumbbell dimers per formula unit. The optical bandgap is 1.12(2) eV and the work function is 5.15(5) eV. First-principles electronic structure calculations using density functional theory (DFT) indicate that this material has potential as a p-type thermoelectric material as it is a narrow bandgap semiconductor, incorporates several heavy elements, and has multiple overlapping bands near the valence band maximum.

Designing heterotropically activated allosteric conformational switches using supercharging.

Heterotropic allosteric activation of protein function, in which binding of one ligand thermodynamically activates the binding of another, different ligand or substrate, is a fundamental control mechanism in metabolism and as such has been a long-aspired capability in protein design. Here we show that greatly increasing the magnitude of a protein's net charge using surface supercharging transforms that protein into an allosteric ligand- and counterion-gated conformational molecular switch. To demonstrate this we first modified the designed helical bundle hemoprotein H4, creating a highly charged protein which both unfolds reversibly at low ionic strength and undergoes the ligand-induced folding transition commonly observed in signal transduction by intrinsically disordered proteins in biology. As a result of the high surface-charge density, ligand binding to this protein is allosterically activated up to 1,300-fold by low concentrations of divalent cations and the polyamine spermine. To extend this process further using a natural protein, we similarly modified Escherichia coli cytochrome b562 and the resulting protein behaves in a like manner. These simple model systems not only establish a set of general engineering principles which can be used to convert natural and designed soluble proteins into allosteric molecular switches useful in biodesign, sensing, and synthetic biology, the behavior we have demonstrated--functional activation of supercharged intrinsically disordered proteins by low concentrations of multivalent ions--may be a control mechanism utilized by Nature which has yet to be appreciated.