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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,NʹE,N,NʹE)-N,Nʹ-([2,2ʹ:5ʹ,2ʺ-terthiophene]-5,5ʺ-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. [ABSTRACT FROM AUTHOR]

Phenyl-substituted perylene diimide (PTCDI-Ph) derivatives are prospective organic, electronic and optoelectronic materials. In this study, the effects of modified intermolecular interactions and molecular conformations on the energy gap and the optical properties of PTCDI-Ph were explored at high pressure and various temperatures by calorimetry, X-ray diffraction, UV-vis absorption, and photoluminescence spectroscopy. Below 498 K, PTCDI-Ph transforms from phase I to phase II, which is stable down to 93 K at least. Above 3.0 GPa, phase II transforms into phase III. The compressed intermolecular distance between perylene cores linearly narrows the band gap, due to the intensified π–π stacking. The negative linear compressibility of the crystal along [100] coincides with the negative thermal expansion in this direction. Owing to the strong pressure and temperature dependence of the luminescence spectrum, the PTCDI-Ph derivatives constitute a promising class of highly stimuli-responsive elastic organic materials with broad potential for tailoring their optoelectronic properties through physical and chemical modifications. [ABSTRACT FROM AUTHOR]

New polymorphs β 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. [ABSTRACT FROM AUTHOR]

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]. [ABSTRACT FROM AUTHOR]

Crystal growth, high-pressure chemistry, kinetic crystallization, nucleation, polymorphism Front Cover: High-pressure Nucleation of Low-Density Polymorphs (Chem. Eur. J. 24/2021) Keywords: crystal growth; high-pressure chemistry; kinetic crystallization; nucleation; polymorphism EN crystal growth high-pressure chemistry kinetic crystallization nucleation polymorphism 6995 6995 1 04/30/21 20210426 NES 210426 B Low-density polymorphs b obtained in a high-pressure environment are reported in this work. [Extracted from the article]