A computational study has been carried out for determining the characteristics of the interaction between one water and hydrogen sulfide molecule with a series of polycyclic aromatic hydrocarbons of increasing size, namely, benzene, anthracene, triphenylene, coronene, circumcoronene, and dicircumcoronene. Potential energy curves were calculated for structures where H(2)X (X=O,S) molecule is located over the central six-membered ring with its hydrogen atoms pointing toward to (mode A) or away from (mode B) the hydrocarbon. The accuracy of different methods has been tested against the results of coupled cluster calculations extrapolated to basis set limit for the smaller hydrocarbons. The spin component scaled MP2 (SCS-MP2) method and a density functional theory method empirically corrected for dispersion (DFT-D) reproduce fairly well the results of high level calculations and therefore were employed for studying the larger systems, though DFT-D seems to underestimate the interaction in hydrogen sulfide clusters. Water complexes in mode A have interaction energies that hardly change with the size of the hydrocarbon due to compensation between the increase in the correlation contribution to the interaction energy and the increase in the repulsive character of the Hartree-Fock energy. For all the other clusters studied, there is a continuous increase in the intensity of the interaction as the size of the hydrocarbon increases, suggesting already converged values for circumcoronene. The interaction energy for water clusters extrapolated to an infinite number of carbon atoms amounts to -13.0 and -15.8 kJ/mol with SCS-MP2 and DFT-D, respectively. Hydrogen sulfide interacts more strongly than water with the hydrocarbons studied, leading to a limiting value of -21.7 kJ/mol with the SCS-MP2 method. Also, complexes in mode B are less stable than the corresponding A structures, with interaction energies amounting to -8.2 and -18.2 kJ/mol for water and hydrogen sulfide, respectively. The DFT-D calculations give values of -16.2 and -9.3 kJ/mol for hydrogen sulfide complexes in modes A and B, less negative than those predicted by the SCS-MP2 method, probably indicating problems with sulfur dispersion parameters.
The interaction of anions with cation-π complexes formed by the guanidinium cation and benzene was thoroughly studied by means of computational methods. Potential energy surface scans were performed in order to evaluate the effect of the anion coming closer to the cation-π pair. Several structures of guanidinium-benzene complexes and anion approaching directions were examined. Supermolecule calculations were performed on ternary complexes formed by guanidinium, benzene, and one anion and the interaction energy was decomposed into its different two- and three-body contributions. The interaction energies were further dissected into their electrostatic, exchange, repulsion, polarization and dispersion contributions by means of local molecular orbital energy decomposition analysis. The results confirm that, besides the electrostatic cation-anion attraction, the effect of the anion over the cation-π interaction is mainly due to polarization and can be rationalized following the changes in the anion-π and the nonadditive (three-body) terms of the interaction. When the cation and the anion are on the same side of the π system, the three-body interaction is anticooperative, but when the anion and the cation are on opposite sides of the π system, the three-body interaction is cooperative. As far as we know, this is the first study where this kind of analysis is carried out with a structured cation as guanidinium with a significant biological interest.
We present our experience with transferring a four-day photometry and dye-adsorption laboratory experiment to the kitchens of students of Applied Thermodynamics from our degree in “Industrial Chemical Process Engineering”. The students designed and built a double-beam photometer using their smartphones and household materials, then prepared a series of dye-solutions with well-known relative concentrations and measured the absorbance–concentration calibration curve. After 24 h of adsorption to kitchen absorbent paper the solutions were visibly decolored. The students were able to determine the equilibrium dye concentrations from absorbance measurements and to calculate the adsorption isotherm. This home-lab experiment allowed them to keep on track with their lessons during the severe lock down in Spain due to COVID-19. They were highly motivated and achieved the learning objectives to a similar degree as in years before with conventional lab equipment.
A systematic study of the interaction of alkaline cations with curved π systems (molecular bowls) derived from fullerene (C(60)) shows the ability of these structures to form stable cation-π complexes with both of their sides: concave and convex. In all cases, complexes with the cation in the convex side are more stable than its corresponding partner inside the bowl. When forming the complexes with the alkaline cations, these bowls exhibit great stability but several descriptors that usually work in planar conjugate molecules (like the magnitude of the charge transferred to the cation or the cation-ligand distance) do not properly describe the trends observed. The present study shows that with these curved π systems inductive effects play a central role in the formation of complexes with alkaline cations. This conclusion contradicts the simplistic point of view on the dominant effect of the electrostatic term in the interaction between alkaline cations and bowls derived from fullerene. Additionally, steric effects can be relevant when bulky cations are placed in the concave side of the largest bowls.
The complexation of the pristine fullerenes C60 and C70 and the endohedral fullerenes Sc3N@C80 and Sc3N@C68 has been tested using a series of hosts of different nature, including the buckybowls corannulene and sumanene, a zinc porphyrin, a chloro boron subphthalocyanine, and a corannulene pentasubstituted with nitrile groups. A systematic theoretical study has been carried out in order to explore both the strength of the interaction and the feasibility for electron transfer of the dimers. Dispersion is the main stabilizing contribution in these dimers, so both molecules orientate so as to maximize the number of close contacts among atoms. As a consequence, all host molecules interact with C70 by the long axis. C60 and Sc3N@C80 are more spherically shaped, so there is no clear preference for the position of the host molecule, though endohedral fullerenes are encapsulated preferentially by the face without contacts with the inner cluster. Complexation energies increase with the contact surface between molecules in the complex. The most stable complexes with fullerenes are formed by the subphthalocyanine and the CN-pentasubstituted corannulene. Depending on the dimer, complexation energies span from around -15 kcal mol of C60 with corannulene to -24 kcal mol of Sc3N@C80 with the subphthalocyanine. Some of the dimers seem to be capable of acting as a donor-acceptor pair, leading to charge transfer states with a neat separation of charge, thus being candidates for organic photovoltaic devices. Endohedral fullerenes are less prone to these donor-acceptor transitions, with charge transfer taking place from the carbon cage to the endohedral cluster. cora5CN, with its inverted polarity, also shows charge transfer upon excitation but with the fullerene acting as a donor and the buckybowl as an acceptor.
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