Crystal structures of three N,N,N′-trisubstituted thioureas for reactivity-controlled nanocrystal synthesis

The synthesis and single-crystal X-ray structures of three N,N,N′-trisubstituted thioureas are reported, namely N,N,N′-tribenzylthiourea, C22H22N2S (1), N-methyl-N,N′-diphenylthiourea, C14H14N2S (2), and N,N-di-n-butyl-N′-phenylthiourea, C15H24N2S (3). The influence of the different substituents on the thioureas is clear from the delocalization of the thiourea C—N and C=S bonds, while the crystal structures show infinite chains of N,N,N′-tribenzylthiourea (1), hydrogen-bonded pairs of N-methyl-N,N′-diphenylthiourea (2) and hexamer ring assemblies of N,N-di-n-butyl-N′-phenylthiourea (3) molecules. The above-mentioned compounds were synthesized via a mild, general procedure, readily accessible precursors and with a high yield, providing straightforward access to a whole library of thioureas.

Infrared Spectra of Hydrogen-Bonded Molecular Complexes Under Spatial Confinement

Infrared (IR) spectroscopy is commonly used in chemical laboratories to study the geometrical structure of molecules and molecular complexes. The analysis of experimental IR spectra can nowadays be reliably supported by the results of quantum-chemical computations as vibrational frequencies and corresponding vibrational transition intensities are routinely calculated using harmonic approximation by virtually all quantum chemistry packages. In the present study we combine the methodology of computing vibrational spectra using high-level electron correlation treatments with an analytical potential-based approach to take into account spatial confinement effects. Using this approach, we perform a pioneering analysis of the impact of the spatial confinement caused by a cylindrical harmonic oscillator potential on the harmonic vibrational transition intensities and frequencies of two hydrogen-bonded complexes: HCN…HCN and HCN…HNC. The emphasis is put on the largest-intensity bands, which correspond to the stretching vibrations. The obtained results demonstrate that embedding the molecular complexes in an external confining potential causes significant changes of transition intensities and vibrational frequencies.

Thermodynamically Stable Cationic Dimers in Carboxyl-Functionalized Ionic Liquids: The Paradoxical Case of “Anti-Electrostatic” Hydrogen Bonding

We show that carboxyl-functionalized ionic liquids (ILs) form doubly hydrogen-bonded cationic dimers (c+=c+) despite the repulsive forces between ions of like charge and competing hydrogen bonds between cation and anion (c+–a−). This structural motif as known for formic acid, the archetype of double hydrogen bridges, is present in the solid state of the IL 1−(carboxymethyl)pyridinium bis(trifluoromethylsulfonyl)imide [HOOC−CH2−py][NTf2]. By means of quantum chemical calculations, we explored different hydrogen-bonded isomers of neutral (HOOC–(CH2)n–py+)2(NTf2−)2, single-charged (HOOC–(CH2)n–py+)2(NTf2−), and double-charged (HOOC– (CH2)n−py+)2 complexes for demonstrating the paradoxical case of “anti-electrostatic” hydrogen bonding (AEHB) between ions of like charge. For the pure doubly hydrogen-bonded cationic dimers (HOOC– (CH2)n−py+)2, we report robust kinetic stability for n = 1–4. At n = 5, hydrogen bonding and dispersion fully compensate for the repulsive Coulomb forces between the cations, allowing for the quantification of the two equivalent hydrogen bonds and dispersion interaction in the order of 58.5 and 11 kJmol−1, respectively. For n = 6–8, we calculated negative free energies for temperatures below 47, 80, and 114 K, respectively. Quantum cluster equilibrium (QCE) theory predicts the equilibria between cationic monomers and dimers by considering the intermolecular interaction between the species, leading to thermodynamic stability at even higher temperatures. We rationalize the H-bond characteristics of the cationic dimers by the natural bond orbital (NBO) approach, emphasizing the strong correlation between NBO-based and spectroscopic descriptors, such as NMR chemical shifts and vibrational frequencies.