Theoretical study of solvent effect on π-EDA complexation II. Complex between TCNE and two benzene molecules
-
O. Kysel’
,
G. Juhász
Abstract
Formation of tetracyanoethylene—benzene 1: 1 and 1: 2 complexes was modeled using the Møller—Plesset second-order theory (MP2) and polarized continuum model (PCM). The MP2 calculated geometry of 1: 1 complex presents a plane-parallel C 2υ sandwich structure with interplanar distance 3.05 × 10−10 m, while the 1: 2 complex has D 2h geometry where the planparallel distance is equal to 3.09 × 10−10 m. The MP2 calculations indicate that the main part of formation enthalpy in both complexes is dispersion energy due to intermolecular electron correlation. The calculations also show that the formation entropy destabilizes both complexes since from the two constituent molecules one complex molecule arises. The MP2/6-31G* procedure showed to be a suitable tool for the estimation of the relative importance of 1: 2 complexation compared to the 1: 1 complexation. In the gas phase the ratio of the equilibrium constants of both complexes K 1:2/K 1:1 = 0.09 was calculated. The presence of solvent, treated by the PCM, further destabilized the 1: 2 complex with respect to the 1: 1 complex. The ratio K 1:2/K 1:1 in CH2Cl2 calculated by the PCM method was 0.022, i.e. the 1: 2 complex was almost 50 times less stable than the 1: 1 complex, which is in agreement with available experimental data. According to the calculations, solvent always destabilizes complex with respect to the isolated (solvated) components.
It was also found that charge polarization in the 1: 2 complex with respect to that in the 1: 1 complex was not strictly additive due to the presence of the second benzene molecule in the 1: 2 complex. Non-additive were also formation enthalpy, entropy, polarizability, charge transfer from donors to acceptor molecule and other properties. This fact is caused by a slightly changed interaction between constituent molecules in the 1: 2 complex in comparison with the 1: 1 complex as well as by the interaction between benzene molecules in the 1: 2 complex which is missing in the 1: 1 complex.
Preliminary CIS/6-31G* theoretical study regarding a few first-electron (electron charge transfer) transitions in both complexes indicates the presence of Frenkel excitn and Davydov transition energy splitting in the 1: 2 “supercomplex” with the first allowed π → π* absorption transition at λ = 355 nm, while the first allowed transition in the case of 1: 1 complex was characterized by λ = 392 nm with the oscillator strength only half of that of the 1: 2 complex, which is in agreement with experiment. These unexpected large hypso-and hypochromic effects predicted by the theory could allow to overcome difficulties of the experimental determination of the 1: 2 complexation.
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© 2007 Institute of Chemistry, Slovak Academy of Sciences
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Articles in the same Issue
- Evaluation and interlaboratory validation of a GC-MS method for analysis of pesticide residues in teas
- Protective effects of vitamin E against CCl4-induced hepatotoxicity in rabbits
- Influence of composition on corroding process of Na2O-K2O-CaO-ZrO2-SiO2 glasses
- Effects of type and number of impellers and liquid viscosity on the power characteristics of mechanically agitated gas—liquid systems
- Modelling of composting of food waste in a column reactor
- Comparison of chemical properties of food products processed by conventional and ohmic heating
- Electrical resistivity and photoluminescence of lead iodide crystals
- Effect of microwave irradiation on the reactivity of chloroarenes in Suzuki—Miyaura reaction
- Kinetics of extraction of coal-tar pitch components with supercritical carbon dioxide
- Mechanism of photocatalytic oxidation of gaseous ethanol
- Kinetics and mechanism of hydroboration of oct-1-and-4-ene by dimeric dialkylboranes
- Reaction sites of N,N′-substituted p-phenylenediamine antioxidants
- Theoretical study of solvent effect on π-EDA complexation II. Complex between TCNE and two benzene molecules
