Origin of the Size-Dependent Stokes Shift in CsPbBr3 Perovskite Nanocrystals.

The origin of the size-dependent Stokes shift in CsPbBr3 nanocrystals (NCs) is explained for the first time. Stokes shifts range from 82 to 20 meV for NCs with effective edge lengths varying from ∼4 to 13 nm. We show that the Stokes shift is intrinsic to the NC electronic structure and does not arise from extrinsic effects such as residual ensemble size distributions, impurities, or solvent-related effects. The origin of the Stokes shift is elucidated via first-principles calculations. Corresponding theoretical modeling of the CsPbBr3 NC density of states and band structure reveals the existence of an intrinsic confined hole state 260 to 70 meV above the valence band edge state for NCs with edge lengths from ∼2 to 5 nm. A size-dependent Stokes shift is therefore predicted and is in quantitative agreement with the experimental data. Comparison between bulk and NC calculations shows that the confined hole state is exclusive to NCs. At a broader level, the distinction between absorbing and emitting states in CsPbBr3 is likely a general feature of other halide perovskite NCs and can be tuned via NC size to enhance applications involving these materials.

(µ2-2-Meth-oxy-ethanol-κ(3) O (1):O (1),O (3))(2-meth-oxy-ethanol-κO (1))tris-(µ2-3,4,5,6-tetra-fluoro-o-phenyl-ene-κ(2) C (1):C (2))trimercury(II).

In the title compound, [Hg3(C6F4)3(C3H8O2)2], two O atoms from one 2-meth-oxy-ethanol ligand and one O atom from the second 2-meth-oxy-ethanol ligand coordinate three Hg(II) atoms [Hg-O = 2.765 (7)-2.890 (8) Å] in the trimeric organomercurial Lewis acid (o-C6F4Hg)3. The hy-droxy groups are involved in formation of intra- and inter-molecular O-H⋯O hydrogen bonds; the latter link two mol-ecules into centrosymmetric dimers. An extensive net of weak inter-molecular C-H⋯F inter-actions further consolidates the crystal packing.

Crystal structure of 8-hy-droxy-quinoline: a new monoclinic polymorph.

In an attempt to grow 8-hy-droxy-quinoline-acetamino-phen co-crystals from equimolar amounts of conformers in a chloro-form-ethanol solvent mixture at room temperature, the title compound, C9H7NO, was obtained. The mol-ecule is planar, with the hy-droxy H atom forming an intra-molecular O-H⋯N hydrogen bond. In the crystal, mol-ecules form centrosymmetric dimers via two O-H⋯N hydrogen bonds. Thus, the hy-droxy H atoms are involved in bifurcated O-H⋯N hydrogen bonds, leading to the formation of a central planar four-membered N2H2 ring. The dimers are bound by inter-molecular π-π stacking [the shortest C⋯C distance is 3.2997 (17) Å] and C-H⋯π inter-actions into a three-dimensional framework. The crystal grown represents a new monoclinic polymorph in the space group P21/n. The mol-ecular structure of the present monoclinic polymorph is very similar to that of the ortho-rhom-bic polymorph (space group Fdd2) studied previously [Roychowdhury et al. (1978 ▶). Acta Cryst. B34, 1047-1048; Banerjee & Saha (1986 ▶). Acta Cryst. C42, 1408-1411]. The structures of the two polymorphs are distinguished by the different geometries of the hydrogen-bonded dimers, which in the crystal of the ortho-rhom-bic polymorph possess twofold axis symmetry, with the central N2H2 ring adopting a butterfly conformation.

Supramolecular synthesis based on piperidone derivatives and pharmaceutically acceptable co-formers.

The target complexes, bis{(E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-oxopiperidinium} butanedioate, 2C27H36N3O(+)·C4H4O4(2-), (II), and bis{(E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-oxopiperidinium} decanedioate, 2C27H36N3O(+)·C10H16O4(2-), (III), were obtained by solvent-mediated crystallization of the active pharmaceutical ingredient (API) (E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-piperidone and pharmaceutically acceptable dicarboxylic (succinic and sebacic) acids from ethanol solution. They have been characterized by melting point, IR spectroscopy and single-crystal X-ray diffraction. For the sake of comparison, the structure of the starting API, (E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-piperidone methanol monosolvate, C27H35N3O·CH4O, (I), has also been studied. Compounds (II) and (III) represent salts containing H-shaped centrosymmetric hydrogen-bonded synthons, which are built from two parallel piperidinium cations and a bridging dicarboxylate dianion. In both (II) and (III), the dicarboxylate dianion resides on an inversion centre. The two cations and dianion within the H-shaped synthon are linked by two strong intermolecular N(+)-H···(-)OOC hydrogen bonds. The crystal structure of (II) includes two crystallographically independent formula units, A and B. The cation geometries of units A and B are different. The main N-C6H4-C=C-C(=O)-C=C-C6H4-N backbone of cation A has a C-shaped conformation, while that of cation B adopts an S-shaped conformation. The same main backbone of the cation in (III) is practically planar. In the crystal structures of both (II) and (III), intermolecular N(+)-H···O=C hydrogen bonds between different H-shaped synthons further consolidate the crystal packing, forming columns in the [100] and [101] directions, respectively. Salts (II) and (III) possess increased aqueous solubility compared with the original API and thus enhance the bioavailability of the API.

N,N-Diethyl-4-[(E)-(pyridin-3-yl)diazen-yl]aniline.

The mol-ecule of the title compound, C15H18N4, adopts a trans conformation with respect to the diazo N=N bond. The dihedral angle between the benzene and pyridine rings in the mol-ecule is 8.03 (5)°. In the crystal, a weak C-H⋯π inter-action arranges the mol-ecules into a corrugated ribbon, with an anti-parallel orientation of neighboring mol-ecules propagating in the [100] direction.

Pyridine-4-carbaldehyde-fumaric acid (2/1).

In the title co-crystal, 2C6H5NO·C4H4O4, two crystallographically different hydrogen-bonded trimers are formed, one in which the components occupy general positions, and one generated by an inversion centre. This results in the uncommon situation of Z = 3 for a triclinic crystal. In the formula units, mol-ecules are linked by O-H⋯N hydrogen bonds.

3,4-Di-amino-pyridinium hydrogen malonate.

In the title salt, C5H8N3 (+)·C3H3O4 (-), the 3,4-di-amino-pyridinium cation is almost planar, with an r.m.s. deviation of 0.02 Å. The conformation of the hydrogen malonate anion is stabilized by an intra-molecular O-H⋯O hydrogen bond, which generates an S(6) ring. In the crystal, N-H⋯O hydrogen bonds link cations and anions into layers parallel to the ab plane.

Pyrimidine-2,4-diamine acetone monosolvate.

In the title compound, C(4)H(6)N(4)·C(3)H(6)O, the pyrimidine-2,4-diamine mol-ecule is nearly planar (r.m.s. deviation = 0.005 Å), with the endocyclic angles covering the range 114.36 (10)-126.31 (10)°. In the crystal, N-H⋯N and N-H⋯O hydrogen bonds link the mol-ecules into ribbons along [101], and weak C-H⋯π inter-actions consolidate further the crystal packing.

Pyridine-2,5-diamine.

In the title mol-ecule, C5H7N3, intra-cyclic angles cover the range 117.15 (10)-124.03 (11)°. The N atoms of the amino groups have trigonal-pyramidal configurations deviating slightly from the pyridine plane by 0.106 (2) and -0.042 (2) Å. In the crystal, the pyridine N atom serves as an acceptor of an N-H⋯N hydrogen bond which links two mol-ecules into a centrosymmetric dimer. Inter-molecular N-H⋯N hydrogen bonds between the amino groups further consolidate the crystal packing, forming a three-dimensional network.

6-Methyl-pyridin-2-amine.

In the title mol-ecule, C6H8N2, the endocyclic angles are in the range 118.43 (9)-122.65 (10)°. The mol-ecular skeleton is planar (r.m.s. deviation = 0.007 Å). One of the two amino H atoms is involved in an N-H⋯N hydrogen bond, forming an inversion dimer, while the other amino H atom participates in N-H⋯π inter-actions between the dimers, forming layers parallel to (100).

Author Correction: Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

The original version of this Article contained an error in the spelling of the author Joseph S. Manser, which was incorrectly given as Joseph M. Manser. This has now been corrected in both the PDF and HTML versions of the Article.

Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

Mixed halide hybrid perovskites, CH3NH3Pb(I1-x Br x )3, represent good candidates for low-cost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material's optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodide-rich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.Mixed halide hybrid perovskites possess tunable band gaps, however, under illumination they undergo phase separation. Using spectroscopic measurements and theoretical modelling, Draguta and Sharia et al. quantitatively rationalize the microscopic processes that occur during phase separation.

Spatially Non-uniform Trap State Densities in Solution-Processed Hybrid Perovskite Thin Films.

The facile solution-processability of methylammonium lead halide (CH3NH3PbI3) perovskites has catalyzed the development of inexpensive, hybrid perovskite-based optoelectronics. It is apparent, though, that solution-processed CH3NH3PbI3 films possess local emission heterogeneities, stemming from electronic disorder in the material. Herein we investigate the spatially resolved emission properties of CH3NH3PbI3 thin films through detailed emission intensity versus excitation intensity measurements. These studies enable us to establish the existence of nonuniform trap density variations wherein regions of CH3NH3PbI3 films exhibit effective free carrier recombination while others exhibit emission dynamics strongly influenced by the presence of trap states. Such trap density variations lead to spatially varying emission quantum yields and correspondingly impact the performance of both methylammonium lead halide perovskite solar cells and other hybrid perovskite-based devices. Of additional note is that the observed spatial extent of the optical disorder extends over length scales greater than that of underlying crystalline domains, suggesting the existence of other factors, beyond grain boundary-related nonradiative recombination channels, which lead to significant intrafilm optical heterogeneities.

Tuning carrier mobilities and polarity of charge transport in films of CuInSe(x)S(2-x) quantum dots.

CuInSe(x)S(2-x) quantum dot field-effect transistors show p-type, n-type, and ambipolar behaviors with carrier mobilities up to 0.03 cm(2) V(-1) s(-1). Although some design rules from studies of cadmium and lead containing quantum dots can be applied, remarkable differences are observed including a strong gating effect in as-synthesized nanocyrstals with long ligands.