Thioindigo (2-(3-Oxo-1-benzothiophen-2(3H)-ylidene)-1-benzothiophen-3(2H)-one) is a synthetic dye related to the natural compound Indigo. Notwithstanding the interest aroused recently by its employment as a functional material in a number of applications, a satisfactory characterization of its solid state is still missing. In this work, we study the occurrence of the two thioindigo α and β polymorphs under various growth conditions, and find that their structural similarity implies they often coexist. However, whereas polymorph β is certainly predominant in the bulk phase, polymorph α grows preferentially on substrates, turning out to be the surface stabilized phase in highly homogeneous and ordered films obtained by the bar-assisted meniscus shearing method (BAMS). DFT calculations support the experimental findings, aiding in the polymorph spectroscopic identification and to the interpretation of the order in the films of polymorph α.

The effect of the solid solution composition on the kinetics of solid-state [2 + 2] photocycloadditions was evaluated via a combination of single crystal XRD, FTIR, Raman spectroscopy, and principal component analysis (PCA).

The discovery of new polymorphs opens unique applications for molecular materials, as the physical properties are predominantly influenced by the crystal structure type. Deposition of molecules at surfaces offers a...

tBoc-quinacridone films obtained by the spin coating and bar‐assisted meniscus shearing methods were subjected to thermal deprotection to recover the organic semiconductor quinacridone in its crystalline form. We found that...

In homogeneous solid-state reactions, the single-crystal nature of the starting material remains unchanged, and the system evolves seamlessly through a series of solid solutions of reactant and product. Among [2 + 2] photodimerizations of cinnamic acid derivatives in the solid state, those involving salts of the 4-aminocinnamic acid have been recognized to proceed homogeneously in a "single-crystal-to-single-crystal" fashion by X-ray diffraction techniques. Here the bromide salt of this compound class is taken as a model system in a Raman spectroscopy study at low wavelengths, to understand how such a mechanism defines the trend of the crystal lattice vibrations during the reaction. Vibrational mode calculations, based on dispersion corrected DFT simulations of the crystal lattices involved in the transformation, have assisted the interpretation of the experiments. Such an approach has allowed us to clarify the spectral signatures and to establish a correlation between the dynamics of the monomer and dimer systems in a process where chemical progress and crystal structural changes are demonstrated to occur simultaneously.