Madhavan Jaccob

Pyrene Schiff base: photophysics, aggregation induced emission, and antimicrobial properties.

Pyrene containing Schiff base molecule, namely 4-[(pyren-1-ylmethylene)amino]phenol (KB-1), was successfully synthesized and well characterized by using (1)H, (13)C NMR, FT-IR, and EI-MS spectrometry. UV-visible absorption, steady-state fluorescence, time-resolved fluorescence, and transient absorption spectroscopic techniques have been employed to elucidate the photophysical processes of KB-1. It has been demonstrated that the absorption characteristics of KB-1 have been bathochromatically tuned to the visible region by extending the π-conjugation. The extended π-conjugation is evidently confirmed by DFT calculations and reveals that π→π* transition is the major factor responsible for electronic absorption of KB-1. The photophysical property of KB-1 was carefully examined in different organic solvents at different concentrations and the results show that the fluorescence of this molecule is completely quenched due to photoinduced electron transfer. Intriguingly, the fluorescence intensity of KB-1 increases enormously by the gradual addition of water up to 90% with concomitant increase in fluorescence lifetime. This clearly signifies that this molecule has aggregation-induced emission (AIE) property. The mechanism of AIE of this molecule is suppression of photoinduced electron transfer (PET) due to hydrogen bonding interaction of imine donor with water. A direct evidence of PET process has been presented by using nanosecond transient absorption measurements. Further, KB-1 was successfully used for antimicrobial and bioimaging studies. The antimicrobial studies were carried out through disc diffusion method. KB-1 is used against both Gram-positive (Rhodococcus rhodochrous and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacterial species and also fungal species (Candida albicans). The result shows KB-1 can act as an excellent antimicrobial agent and as a photolabeling agent. S. aureus, P. aeruginosa, and C. albicans were found to be the most susceptible microorganisms at 1 mM concentration among the bacteria used in the present investigation.

Ultrasonic, spectrophotometric and theoretical studies of sigma and PI interactions of iodine with substituted benzene

The charge transfer (CT) interaction between three structurally different benzenoid compounds (donors), namely, chlorobenzene (1), phenol (2), anisole (3), and iodine (I2, acceptor) were investigated by experimental methods (ultrasonic and UV-Visible analysis) and theoretical calculations. Notably, strong solute–solute interactions and the existence of a CT type of interaction between 1–3 and I2 is clearly analyzed from the trend in acoustical and excess thermo acoustical parameters with concentration at 303 K in an n-hexane medium. The formation of 1 : 1 complexes between iodine and 1–3 was established by the UV-visible spectroscopic method. The structure and stabilization energies of 1–3 and I2 were further calculated by DFT calculations. Among the σ- and π-type interactions, a π-type complex (1a–3a) with an atom-centered orientation is found to be the preferred and stable geometry for all the CT complexes. The stability constant of the CT complexes was calculated by spectroscopic and ultrasonic methods, which show a similar trend with the DFT computed stabilization energies. Furthermore, AIM and NBO analyses were used to quantify the nature of the stabilizing interactions that exist in 1–3 and the I2 CT complexes. Our computed results are in good agreement with the experimental observations.

Role of Anation on the Mechanism of Proton Reduction Involving a Pentapyridine Cobalt Complex: A Theoretical Study

Kinetic and thermodynamic aspects of proton reduction involving pentapyridine cobalt(II) complex were investigated with the help of quantum chemical calculations. Free energy profile of all possible mechanistic routes for proton reduction was constructed with the consideration of both anation and solvent bound pathways. The computed free energy profile shows that acetate ion plays a significant role in modulating the kinetic aspects of Co(III)-hydride formation which is found to be the key intermediate for proton reduction. Upon replacing solvent by acetate ion, one electron reduction and protonation of CoI species become more rapid along with slow displacement reaction. Most favorable pathways for hydrogen evolution from Co(III)-hydride species is also investigated. Among the four possible pathways, reduction followed by protonation of Co(III)-hydride (RPP) is found to be the most feasible pathway. On the basis of QTAIM and NBO analyses, the electronic origin of most favorable pathway is explained. The basicity of cobalt center along with thermodynamic stability of putative CoIII/II-H species is essentially a prime factor in deciding the most favorable pathway for hydrogen evolution. Our computed results are in good agreement with experimental observations and also provided adequate information to design cobalt-based molecular electrocatalysts for proton reduction in future.