Non-covalent interactions

This review describes how non-covalent interactions, such as hydrogen (inter-and intramolecular, resonance-and charge-assisted hydrogen bonding), halogen, chalcogen and pnicogen bonds, p-interactions, as well as other types of weak forces can influence and control the reactions in the synthesis, e.g., of metal-containing supramolecular networks, providing a class of highly directional stabilizing contacts that can be exploited in the design of coordination compounds. The selected recent examples show that both inter-and intramolecular non-covalent interactions can influence the formation of coordination compounds. This overview of non-covalent interactions applied for synthesis and design of coordination compounds also contributes to an improved understanding of their behavior in crystal engineering, catalysis, etc. It provides a practical consultation for synthetic chemists that are interested in exploring and further developing non-covalent interactions assisted synthesis and design of coordination compounds.

This paper is a logical continuation of the theoretical survey of the CH⋯O/N specific contacts in the nucleobase pairs using a wide arsenal of the modern methods, which was initiated in our previous study [J. Biomol. Struct. & Dynam., 2014, 32, 993–1022]. It was established that 34 CH⋯O and 7 CH⋯N interactions, that were detected by quantum-chemical calculations in the 39 biologically important pairs involving modified nucleobases, completely satisfy all geometrical, vibrational, electron-topological, in particular Bader’s and “two-molecule” Koch and Popelier’s, Grunenberg’s compliance constants theory and natural bond orbital criteria indicating that they can be identified as true H-bonds. The geometrical criteria of the H-bond formation are fulfilled for all considered CH⋯O/N H-bonds without any exception. It was shown that the classical rule of the stretching vibration shifts does not work in the ~95% cases of the CH⋯O/N H-bonds. Furthermore, significant increase in the frequency of the out-of-plane deformation modes γ(CH) under the formation of CH⋯O/N H-bonds and corresponding changes of their intensities can be also considered as reliable indicators of the H-bonding. We revealed high linear mutual correlations between the electron density, Laplacian of the electron density, H-bond energy at the (3, −1) bond critical points of the CH⋯O/N H-bonds, and different physico-chemical parameters of the CH⋯O/N H-bonds. We suggested that the electron density ρ and the interaction energy E(2) of the lone orbital pairs are the most reliable descriptors of the H-bonding. The linear dependence of the H-bond energy ECH⋯O/N on the electron density ρ was established: ECH⋯O = 250.263∙ρ – .380/258.255∙ρ – .396 and ECH⋯N = 196.800∙ρ – .172/268.559∙ρ – .703 obtained at the density functional theory (DFT)/Møller−Plesset (MP2) levels of theory, respectively. The studies of the interaction energies show that the contribution of the CH⋯O and CH⋯N H-bonds into the base pairs stability varies from 3.0/4.2 to 35.1/31.2% and from 3.0/4.3 to 44.4/46.5% at the DFT/MP2 levels of theory, accordingly. Energy decomposition analysis performed for all base pairs involving canonical and modified nucleobases defines the electrostatic attraction and Pauli repulsion as dominant stabilizing forces in all complexes. This observation was additionally confirmed by the results of the QTAIM delocalization indexes analysis. The studies reported here advance our understanding of the biological role of the weak CH⋯O/N H-bonds, that dictates the requirements for the structural and dynamical similarity of the canonical and mismatched pairs with Watson–Crick (WC) geometry, which facilitates their enzymatic incorporation into the DNA double helix during DNA replication. Thus, these H-bonds in the base pairs with WC geometry may be also considered as “the last drop” at the transmission of the electronic signal that launches the chemical incorporation of the incoming nucleoside triphosphate into DNA.

Composites of linear-low density polyethylene (LLDPE) with multi-walled carbon nanotubes (MWCNT) and thermally reduced graphene (TRGO) were produced by melt compounding. The composites were compatibilized by grafting aromatic pyridine groups onto the LLDPE backbone. The aromatic moieties established non-covalent π-π interactions with the carbon nanostructures, thus allowing for efficient dispersion, without compromizing their electrical properties. By using identical matrices, it was possible to investigate the effects of filler geometry on the electrical, mechanical and rheological properties of the composites. The 1-D nature and smaller surface area of the MWCNT facilitated their dispersion within the polymer matrix, whereas the graphene agglomerates appeared to breakup through an erosion mechanism. The resulting mixture of aggregates and individual graphene platelets favored lower electrical and rheological percolation thresholds. However the maximum electrical conductivity achieved in the TRGO/LLDPE was lower by about an order of magnitude compared to the MWCNT/LLDPE composites, probably due to residual oxygen in the graphene’s structure. TRGO based composites presented higher moduli at the same filler loadings, while elongations at break were comparable. All composites exhibited time-dependent rheological properties, indicative of their tendency to aggregate. A more pronounced increase in viscoelastic properties was noted in the composites containing TRGO, presumably due to the higher surface area of the graphene platelets, and the presence of larger aggregates.

Graphene was prepared by low temperature vacuum-assisted thermal exfoliation of graphite oxide. The resulting thermally reduced graphene oxide (TRGO) had a specific surface area of 586 m2/g and consisted of a mixture of single-layered and multilayered graphene. The TRGO was added to maleated linear low-density polyethylene LLDPE and to its derivatives with pyridine aromatic groups by melt compounding. The LLDPE/TRGO composites exhibited very low electrical percolation thresholds, between 0.5 and 0.9 vol %, depending on the matrix viscosity and the type of functional groups. The dispersion of the TRGO in the compatibilized composites was improved significantly, due to enhanced noncovalent interactions between the aromatic moieties grafted onto the polymer matrix and the filler. Better dispersion resulted in a slight increase in the rheological and electrical percolation thresholds, and to significant improvements in mechanical properties and thermal conductivity, compared to the noncompatibilized composites. The presence of high surface area nanoplatelets within the polymer also resulted in a substantially improved thermal stability. Compared to their counterparts containing multiwalled carbon nanotubes, LLDPE/TRGO composites had lower percolation thresholds. Therefore, lower amounts of TRGO were sufficient to impart electrical conductivity and modulus improvements, without compromising the ductility of the composites.

The aim of this work is to cast some light on the H-bonds in double-stranded DNA in its AI and BI forms. For this purpose, we have performed the MP2 and DFT quantum chemical calculations of the canonical nucleoside conformers, relative to the AI and BI DNA forms, and their Watson-Crick pairs, which were regarded as the simplest models of the double-stranded DNA. Based on the atoms-in-molecules analysis (AIM), five types of the CH···O hydrogen bonds, involving bases and sugar, were detected numerically from 1 to 3 per a conformer: C2'H···O5', C1'H···O2, C6H···O5', C8H···O5', and C6H···O4'. The energy values of H-bonds occupy the range of 2.3-5.6 kcal/mol, surely exceeding the kT value (0.62 kcal/mol). The nucleoside CH···O hydrogen bonds appeared to "survive" turns of bases against the sugar, sometimes in rather large ranges of the angle values, pertinent to certain conformations, which points out to the source of the DNA lability, necessary for the conformational adaptation in processes of its functioning. The calculation of the interactions in the dA·T nucleoside pair gives evidence, that additionally to the N6H···O4 and N1···N3H canonical H-bonds, between the bases adenine and thymine the third one (C2H···O2) is formed, which, though being rather weak (about 1 kcal/mol), satisfies the AIM criteria of H-bonding and may be classified as a true H-bond. The total energy of all the CH···O nontraditional intramolecular H-bonds in DNA nucleoside pairs appeared to be commensurable with the energy of H-bonds between the bases in Watson-Crick pairs, which implies their possible important role in the DNA shaping.

The effects of electric fields on the filler response dynamics and electrical percolation of poly(ethylene succinate)/multiwall carbon nanotube (MWCNT) composites are studied. When subjected to AC electric fields in their melt state, PESu/MWCNT composites exhibit dramatic improvements in their transverse electrical conductivity. More importantly, the elevated conductivity values are preserved after matrix solidification. Overall, the experimental results show that the electrified composites exhibit the same electrical conductivity levels as their non-electrified counterparts at approximately threefold less filler content. The dynamics of the insulator-to-conductor transition under an electric field also are studied for these composites and correlate reasonably well with operating parameters, such as electric field intensity, matrix viscosity, and filler content through a relatively simple model. Such a model can serve as an enabling tool in the determination of process conditions for the manufacturing of electrically conducting MWCNT/polymer composites.

Reductive amination of 4-iodo-tetrafluorobenzaldehyde 2 and 15N-enriched benzylamine yielded the title compound 1. Single crystal X-ray diffraction (XRD) revealed that the product crystallizes in the triclinic system of the P-1 space group. The structure is consisting of infinite one-dimensional chair like chains, based on intermolecular N􏰀􏰀􏰀I halogen bonding. Only intermolecular weak hydrogen bonds NAH􏰀􏰀􏰀F and CAH􏰀􏰀􏰀F are observed. Representative XRD data have been compared to the results of theoretical semi- empirical calculations in the solid-state obtained using the PM6 method. Charges of I, N and F atoms are calculated from Natural Bond Orbital (NBO) and Electrostatic Potential Surface maps have been esti- mated by applying second-order Møller–Plesset (MP2) perturbation theory, and confirmed clearly the assumption of r-hole bonding formation.

The objectives of this work are to quantify the degree of multiwalled carbon nanotube (MWCNT) length reduction upon melt compounding and to demonstrate unambiguously that the length reduction is mainly responsible for the increase in electrical percolation threshold of the resulting composites. Polyolefin matrices of varying viscosities and different functional groups are melt compounded with MWCNTs. A simple method is developed to solubilize the polymer matrix and isolate the MWCNTs, enabling detailed imaging analysis. In spite of the perceived strength of the MWCNTs, the results demonstrate that the shear forces developed during melt mixing are sufficient to cause significant nanotube breakage and length reduction. Breakage is promoted when higher MWCNT contents are used, due to increased probability of particle collisions. Furthermore, the higher shear forces transmitted to the nanotubes in the presence of higher matrix viscosities and functional groups that promote interfacial interactions, shift the nanotube distribution toward smaller sizes. The length reduction of the MWCNTs causes significant increases in the percolation threshold, due to the loss of interconnectivity, which results in fewer conductive pathways. These findings are validated by comparing the experimental percolation threshold values with those predicted by the improved interparticle distance theoretical model.