Francisco Javier Zúñiga

1H-Benzotriazole crystallizes as two different polymorphs, namely 4aα and 4aβ. One polymorph is chiral and it resolves spontaneously as conglomerates. The other polymorph crystallizes in a centrosymmetric space group and it is therefore achiral. In both polymorphs supramolecular structures are formed starting from achiral monomers. An analysis of these two polymorphs of 1H-benzotriazole has been carried out by a complete strategy involving different solid-state experimental techniques and quantum chemical calculations (DFT, Density Functional Theory). In particular, X-ray crystallography, NMR spectroscopy and vibrational spectroscopy techniques (FarIR, IR and Raman) that are not sensitive to chirality have been used to characterize the two polymorphs structurally. Vibrational spectroscopy (VCD, Vibrational Circular Dichroism) that is sensitive to chirality was employed to determine the absolute configuration (M or P helices) of the chiral supramolecular structure of 4aα.

This paper reports on the polymorphism of 2-propyl-1H-benzimidazole (2PrBzIm) induced by temperature change. Upon heating, an irreversible reconstructive-type phase transition atT= 384 K from the ordered formI(P2₁2₁2₁) to a new polymorph, formII_HT(Pcam), was observed. The structural transformation between formsIandIIinvolves significant changes in the crystal packing, as well as a key conformational variation around the propyl chain of the molecule. After the first irreversible phase transition, theII_HTform undergoes two further (reversible) phase transitions upon cooling at 361 K (II_RT) and 181 K (II_LT). All three phases (formsII_HT,II_RTandII_LT) have almost identical crystal packing and, given the reversibility of the conversions as a function of temperature, they are referred to as formIItemperature phases. They differ, however, with respect to conformational variations around the propyl chain of 2PrBzIm. Energy calculations of the gas-phase conformational energy landscape of this compound about its flexible bonds allowed us to classify the observed conformational variations of all forms into changes and adjustments of conformers. This reveals that formsIandIIare related by conformational change, and that two of the formIIphases (HT and RT) are related by conformational adjustment, whilst the other two (RT and LT) are related by conformational change. We introduce the term `conformational phases' for different crystal phases with almost identical packing but showing changes in conformation.

2-Propyl-1H-benzimidazole (2PrBzIm) is a small molecule, commercially available, which displays a curious behavior in the solid state. 2PrBzIm, although devoid of chirality by fast rotation about a single bond of the propyl group in solution, crystallizes as a conglomerate showing chiroptical properties. An exhaustive analysis of its crystal structure and a wide range of experiments monitored by vibrational circular dichroism spectroscopy eliminated all possibilities of an artifact. What remains is a new example of the unexplained phenomenon of persistent supramolecular chirality.

Peptides can assemble to supramolecular structures, of which fibers are of special biochemical and medical relevance. We employed Raman and infrared spectroscopy to elucidate the chemical integrity of fibers built from peptides and peptide derivates that contain the aromatic side groups fluorenyl and phenyl. Because the observed spectra compare very well with simulation results of the respective single molecules in vacuum, we were able to assign all observed vibrations. We found the main differences between solid phase and single molecule for O‐H and N‐H stretching and bending vibrations, owing to hydrogen bonding in solids. The fluorenyl and phenyl residues cause π‐stacking of the molecules, which barely manifests in the spectra, but clearly in the structures. Whereas hydrogen bonds provide the principal stability of the fiber backbone, aromatic π‐stacking supports the assembly to fibers, especially when electrospinning assists the molecular alignment. Copyright © 2012 John Wiley & Sons, Ltd.