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By fluorescence spectroscopy it has been established that coal derived asphaltene (CDA) forms aggregates in CCl4medium. The new feature of this compound is that even before aggregate formation it can incorporate water molecules and the critical aggregation concentration (CAC) in nonaqueous medium increases with increase in ω (= water:CDA mole ratio). The fluorescence spectroscopic determination of the equilibrium constant (K) of the molecular complex of [60] fullerenes with CDA in carbon tetrachloride medium has revealed thatKincreases on addition of microquantities of water. This observation has been rationalized by assuming that the nitrogenatoms at one end of CDA molecules attach themselves to the water micropool and thus producing a different conformation with a wider distance at the other end. This pre-organization further facilitates inclusion. By utilizing fluorescence variation of [60]fullerene/CDA complex in CCl4as continuous medium with change in ω a critical ω (=5) has been found. The formation of CDA/[60]fullerene complex has also been established by NMR spectroscopy. [ABSTRACT FROM PUBLISHER]

Coal-derived asphaltene (CDA) has been shown to form electron donor–acceptor-type molecular complexes with electron acceptor such as 2,5-cyclohexadiene-1,4-diylidene also known as tetracyanoquinodimethane (TCNQ) in homogeneous medium of carbon tetrachloride and heterogeneous medium of aqueous SDS. This has been investigated both by UV-Vis and fluorescence spectrophotometric method. The Charge transfer (CT) absorption peaks have been detected by difference spectral method and the wavelengths of the CT peaks are close in both the medium. The formation constants (K) have been determined using the Benesi–Hildebrand equation. The magnitudes ofKare in the order of 103 L mol−1that are comparable to some supramolecular or inclusion complexes. The study reveals the presence of π-donor (i.e., aromatic) type of compounds in CDA molecule. It also supports the view that CDA molecules exist in solution forming micellar aggregate, in the cavities of which the TCNQ molecules are included. The remarkable increase (three fold) in the formation constant in the SDS medium compared to CCl4further indicates that the CDA aggregate in SDS undergoes some preorganization to further facilitate inclusion. [ABSTRACT FROM PUBLISHER]

Highlights: [•] Coal derived asphaltene (CDA) forms molecular complex with [60]-, [70]fullerene in CCl4 medium. [•] The order of complexation for CDA:[60]fullerene is 2:1 and for CDA:[70]fullerene is 3:1. [•] Respective charge transfer absorption peaks have been detected by difference spectral method. [•] The values of Δ calculated indicate that the complexation process in both the cases is predominantly entropy-driven. [ABSTRACT FROM AUTHOR]

The structure of coal derived asphaltene (CDA) proposed by Mullins et al has been corroborated through theoretical and experimental examination by the virtue of its electron donor property. Here, o -chloranil has been used as an electron acceptor. Investigation of o -chloranil/CDA complex in gas phase has been performed by density functional theory (DFT) methods. The Charge transfer (CT) transition energy of the complex in gas phase was calculated by the time-dependent density function theory (TD-DFT) using the ground state optimized geometry at the respective levels of theory. For this, the three semi empirical methods AM1, PM3 and PM3MM were computed under the MPW1PW91, B3PW91, PBE1PBE, BPV86 and RCIS formalism. It is found that the two formalisms MPW1PW91 and PBEPBE under PM3 and PM3MM reproduced values close to the experimental one. However, all of them provide lower charge transfer (CT) transition energy values than that has been experimentally determined. Experimentally, FTIR spectra of the donor, acceptor and the complex further supported the understanding of complex formation and demonstrated close similarity with the theoretically determined CDA frequencies. These findings support the validity of the CDA structure to an extent. [ABSTRACT FROM AUTHOR]