Non-covalent interactions in solution

Non-covalent interactions taking place in solution are essential in chemical and biological systems. The solvent environment plays an important role in determining the geometry and stability of interactions. This thesis examines aromatic stacking interactions, alkyl-alkyl interactions, edge-to-face aromatic interactions, halogen bonds and hydrogen…hydrogen interactions in solution. Chapter 1 briefly introduces the different classes of non-covalent interactions, in addition to the state-of-the-art models and methods for investigating these weak interactions. The chapter finishes with a focus on dispersion interaction in alkanes and arenes. Chapter 2 investigates dispersion interactions between stacked aromatics in solution using a new class of complexes and thermodynamic double mutant cycles (DMCs). In extended aromatics, dispersion was detected as providing a small but significant contribution to the overall stacking free energies. Chapter 3 concerns the experimental measurement of alkyl-alkyl dispersion interactions in a wide range of solvents using Wilcox torsion balances. The contribution of dispersion interactions to alkyl-alkyl association was shown to be very small, with DMC, QSPR method and Hunter's solvation model. Chapter 4 studies edge-to-face aromatic interactions in series of solvents. In the open system, edge-to-face aromatic interactions were found to be sensitive to the solvent environment. The solvent effects were complicated and cannot be rationalised by a single parameter. Further analysis is needed. Chapter 5 describes a preliminary approach to investigate organic halogen…π interactions in solution using supramolecular complexes and torsion balances. Chapter 6 is a preliminary investigation of the ability of hydrogen atoms to act as H bond acceptors in silane compounds. Computations and 1H NMR demonstrated a weak interaction between silane and perfluoro-tert-butanol

Damage Characteristics of Argillaceous Quartz Sandstone Mesostructure under Different Wetting-drying Conditions

Extensive water–rock interaction in the Three Gorges Reservoir area of the Yangtze River leads to rock mass deterioration along the reservoir banks. However, mineral evolution behavior and its effect on the mesostructure deterioration of rocks under the wetting–drying cycle condition remain unknown. So, the wetting–drying cycle tests were conducted on peculiar argillaceous quartz sandstone in TGRA under neutral (pH = 7) and alkaline (pH = 10) water environments. Here, we provided detailed physical and microscopy images data to determine the control mechanism of mineral behavior on the evolution of sandstone’s mesostructure. Under the neutral condition, repeated “absorption and swelling–dehydration and contraction” of clay minerals leads to the repeated physical action of “squeezing–unloading” in the interior of a rock. This results in the initiation and gradual expansion of cracks in the framework mineral quartz, exhibiting failure mode from the interior to the exterior. In contrast, under the alkaline condition, the dissolution on the surface of quartz particles leads to the expansion and connection of pores, implying that the sandstone exhibits failure mode from the exterior to the interior. Moreover, the internal mechanical analysis indicates the minerals are at high pressure because of the expansion of clay minerals in the neutral solution. However, in an alkaline water environment, the extrusion pressure of framework mineral quartz decreases significantly and is not easily broken due to increased porosity. Thus, the evolution behavior of minerals in different water environments plays an important role in the damage of the rock

Restricting shuttling in bis(imidazolium)…pillar[5]arene rotaxanes using metal coordination

Metal coordination to a series of bis(imidazolium)…pillar[5]arene [2]rotaxanes through the formation of metal-carbene bonds facilitates a new strategy to restrict the shuttling motion in [2]rotaxanes. Whereas the pillar[5]arene macrocycle rapidly shuttles along the full length of the bis(imidazolium) rod for the parent [2]rotaxane, Ag(I) coordination to the imidazolium groups through the formation of N-heterocyclic carbenes leads to restricted motion, effectively confining the shuttling motion of the [2]rotaxane. The Ag(I) coordinated [2]rotaxanes can be reacted further, either removing the Agcarbene species to recreate the parent [2]rotaxane, or reaction with more bulky Pd(II) species to further restrict the shuttling motion through steric inhibition

Synthesis and characterisation of rylene diimide dimers using molecular handcuffs

A strategy for positioning, and loosely connecting, molecules in close proximity using mechanically interlocked handcuffs is described. The strategy is demonstrated using rylene diimides, creating dimeric structures in which two components are linked through pillar[5]arene/imidazolium rotaxanes. Investigation of the resulting molecules demonstrates intriguing and new properties that arise from placing these redox active dye molecules together, allowing interactions, whilst allowing the molecules to separate as required. In particular we observe excimer emission from a perylene diimide dimer handcuff and the formation of an unusual radical anion π-dimer upon double reduction of the same molecule. The latter exhibits a unique visible absorption profile for a PDI-based molecule. We demonstrate the flexibility of our approach by making an unprecedented mixed perylene diimide/naphthalene diimide dimer which also reveals interactions between the two components. Our synthetic strategy facilitates the creation of unusual dimeric structures and allows the investigation of intermolecular interactions and the effects they have on electronic and magnetic properties

van der Waals-induced chromatic shifts in hydrogen-bonded two-dimensional porphyrin arrays on boron nitride

The fluorescence of a two-dimensional supramolecular network of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) adsorbed on hexagonal boron nitride (hBN) is red shifted due to, primarily, adsorbate–substrate van der Waals interactions. TCPP is deposited from solution on hBN and forms faceted islands with typical dimensions of 100 nm and either square or hexagonal symmetry. The molecular arrangement is stabilized by in-plane hydrogen bonding as determined by a combination of molecular resolution atomic force microscopy performed under ambient conditions and density functional theory; a similar structure is observed on MoS2 and graphite. The fluorescence spectra of submonolayers of TCPP on hBN are red-shifted by ∼30 nm due to the distortion of the molecule arising from van der Waals interactions, in agreement with time-dependent density functional theory calculations. Fluorescence intensity variations are observed due to coherent partial reflections at the hBN interface, implying that such hybrid structures have potential in photonic applications

Quantifying Solvophobic Effects in Non-polar Cohesive Interactions

The hydrophobic effect plays a central role in determining the structure, activity, and properties of biomolecules and materials. In contrast, the general manifestation of this phenomenon in other solventsthe solvophobic effectalthough widely invoked, is currently poorly defined because of the lack of a universally accepted descriptor. Here we have used synthetic molecular balances to measure solvent effects on aromatic, aliphatic, and fluorous nonpolar interactions. Our solvent screening data combined with independent experimental measurements of supramolecular association, single-molecule folding, and bulk phase transfer energies were all found to correlate well with the cohesive energy density (<i>ced</i>) of the solvent. Meanwhile, other measures of solvent cohesion, such as surface tension and internal pressure, gave inferior correlations. Thus, we establish <i>ced</i> as a readily accessible, quantitative descriptor of solvophobic association in a range of chemical contexts

Can dispersion forces govern aromatic stacking in an organic solvent?

.xyx coordinates of minimised complex geometries, NMR characterisation and titration data.Experimental support for the dominance of van der Waals dispersion forces in aromatic stacking interactions occurring in organic solution is surprisingly limited. Here, we have examined the size-dependence of aromatic stacking in an organic solvent. The interaction energy was found to vary by ~7.5 kJ mol–1 on going from a phenyl-phenyl to an anthracene-pyrene stack. Strikingly, the experimental data were highly correlated with dispersion energies determined using symmetry-adapted perturbation theory (SAPT), while the induction, exchange, electrostatic and solvation energy components correlated poorly. Both the experimental data and the SAPT-dispersion energies gave high-quality correlations with the change in solvent accessible area upon complexation. Thus, the size-dependence of aromatic stacking interactions is consistent with the dominance of van der Waals dispersion forces even in the presence of a competing polarizable solvent.Cockroft, Scott; Yang, Lixu. (2015). Can dispersion forces govern aromatic stacking in an organic solvent?, 2009-2015 [dataset]. University of Edinburgh. EaStCHEM School of Chemistry. http://dx.doi.org/10.7488/ds/326