Unprecedented Richness of Temperature- and Pressure-Induced Polymorphism in 1D Lead Iodide Perovskite.

Inherent features of metal halide perovskites are their softness, complex lattice dynamics, and phase transitions spectacularly tuning their structures and properties. While the structural transformations are well described and classified in 3D perovskites, their 1D analogs are much less understood. Herein, both temperature- and pressure-dependent structural evolutions of a 1D AcaPbI3 perovskitoid incorporating acetamidinium (Aca) cation are examined. The study reveals the existence of nine phases of δ-AcaPbI3, which present the most diverse polymorphic collection among known perovskite materials. Interestingly, temperature- and pressure-triggered phase transitions in the 1D perovskotoid exhibit fundamentally different natures: the thermal transformations are mainly associated with the collective translations of rigid polyanionic units and ordering/disordering dynamics of Aca cations, while the compression primarily affects inorganic polymer chains. Moreover, in the 1-D chains featuring the face-sharing connection mode of the PbI6 octahedra the Pb···Pb distances are significantly shortened compared to the corner-sharing 3D perovskite frameworks, hence operating in the van der Waals territory. Strikingly, a good correlation is found between the Pb···Pb distances and the pressure evolution of the bandgap values in the δ-AcaPbI3, indicating that in 1D perovskitoid structures, the contacts between Pb2+ ions are one of the critical parameters determining their properties.

High-pressure Nucleation of Low-Density Polymorphs*.

New polymorphs ß and γ of bis-3-nitrophenyl disulphide, crystallized above 0.3 GPa, are less dense than the ambient-pressure polymorph α. This counterintuitive density relation results from the high-entropy nucleation and subsequent kinetic crystallization. The work performed by pressure compensates the high entropy and temperature product, substantiated in varied conformers and increased chemical potential. Pressure-increased viscosity promotes the kinetic polymorphs, in accordance with empirical Ostwald's rule of stages. It contrasts to mechanochemical techniques, favouring high-density polymorphs.

High-pressure Nucleation of Low-Density Polymorphs.

Invited for the cover of this issue is the group of Andrzej Katrusiak at Adam Mickiewicz University. The image depicts a wave and the sun, which represent the high energy required for the high-entropy nucleation reported in this work. Read the full text of the article at 10.1002/chem.202005121.

A new look at imines and their mixture with PC71BM for organic, flexible photovoltaics.

Due to its high electron affinity and electron mobility in a wide absorption range of the visible solar spectrum, [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) is often used as an efficient acceptor in organic photovoltaics. In turn, imines are additives to the active layer of organic solar cells, mainly due to the free electron pair of the imine nitrogen atom and the presence of various chemical groups affecting the polarity and conformations of molecules. However, the attainable efficiency is not as high as expected. Therefore, we have systematically investigated two imines and their mixtures with PC71BM by spectroscopic (the high pressure UV-Vis and frequency domain dielectric), thermoelectric, and mechanical methods for organic, flexible photovoltaics. Both the imines, (N,N'E,N,N'E)-N,N'-([2,2':5',2"-terthiophene]-5,5"-diylbis(methanylylidene))bis(benzo[d]thiazol-2-imine) (SC3) and (6E)-N-((5-(5-(5-((E)-(4-(4-(4-fluorophenyl)thiazol-2-yl)phenylimino)methyl)thiophen-2-yl)thiophen-2-yl)thiophen-2-yl)methylene)-4-(4-(4-fluorophenyl)thiazol-2-yl)benzenamine (SC13), have the same core composed of three thiophene rings but different terminal chains of the molecules. In the imine SC3, the imine bond is followed by benzothiazole rings on both sides of the core, while in SC13, a thiazole ring separates two benzene rings, the terminal one F-substituted. The difference in molecular structure affects the electric properties of the neat imine and its mixed layers. An addition of PC71BM to the imines improves their electric conductivity. The mechanical studies focused on the stress at break and elongation showed superior behaviour compared to fullerene derivative. High pressure systematically reduces the band gap energy, Eg, from 1.68 eV at 0.16 GPa to 1.51 eV at 2.69 GPa for PC71BM, from 1.77 eV at 0.1 MPa to 1.53 eV at 4.15 GPa for SC3, and from 1.99 eV at 0.11 GPa to 1.8 eV at 3.10 GPa for SC13, as determined by the UV-Vis absorbance measurements in a diamond-anvil cell. These Eg reductions reflect the compressed intermolecular interactions that can be used to monitor the structural stability of these compounds. Based on the dielectric studies it was found that the relaxation processes registered for both imines are probably the grain boundary relaxation. Two processes also appear in the systems with PC71BM, but none of them is the one characteristic of imines. The high-frequency process has a dipole character while the low-frequency one is probably the grain boundary relaxation of these systems. The mechanism of quasi-DC conduction in various temperature ranges in the studied systems was also determined.

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis.

Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access to well-defined materials with complex architecture. However, most photo-ATRP systems can only generate radicals under biocidal UV light and are oxygen-sensitive, hindering their practical use in the synthesis of polymer biohybrids. Herein, inspired by the photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, we demonstrate a dual photoredox/copper catalysis that allows open-air ATRP under green light irradiation. Eosin Y was used as an organic photoredox catalyst (PC) in combination with a copper complex (X-CuII/L). The role of PC was to trigger and drive the polymerization, while X-CuII/L acted as a deactivator, providing a well-controlled polymerization. The excited PC was oxidatively quenched by X-CuII/L, generating CuI/L activator and PC˙+. The ATRP ligand (L) used in excess then reduced the PC˙+, closing the photocatalytic cycle. The continuous reduction of X-CuII/L back to CuI/L by excited PC provided high oxygen tolerance. As a result, a well-controlled and rapid ATRP could proceed even in an open vessel despite continuous oxygen diffusion. This method allowed the synthesis of polymers with narrow molecular weight distributions and controlled molecular weights using Cu catalyst and PC at ppm levels in both aqueous and organic media. A detailed comparison of photo-ATRP with PET-RAFT polymerization revealed the superiority of dual photoredox/copper catalysis under biologically relevant conditions. The kinetic studies and fluorescence measurements indicated that in the absence of the X-CuII/L complex, green light irradiation caused faster photobleaching of eosin Y, leading to inhibition of PET-RAFT polymerization. Importantly, PET-RAFT polymerizations showed significantly higher dispersity values (1.14 ≤ D ≤ 4.01) in contrast to photo-ATRP (1.15 ≤ D ≤ 1.22) under identical conditions.

Large negative linear compressibility of a porous molecular co-crystal.

Flexible and transformable molecules, particularly those responding to external stimuli, are needed for designing sensors and porous compounds capable of storing or separating gases and liquids. Under normal conditions the photochromic compound, 1,2-bis[2-methyl-5-(pyridyl)-3thienyl]cyclopentene (BTCP) forms a porous co-crystal with 1,4-diiodotetrafluorobenzene (dItFB). It traps acetone (Ac) molecules in the pores. Owing to a unique system of pores in the polar framework, the crystal is sensitive to the humidity in the air and to the chosen liquid environment. When compressed in non-penetrating media, the crystal displays a strong negative linear compressibility (NLC) along [100].