title: Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties.
abstract: Spectrophotometric, FTIR and theoretical studies of the charge-transfer complexes between Isoniazid (pyridine-4-carboxylic acid hydrazide) and the acceptors (p-chloranil, chloranilic acid and tetracyanoethylene) in acetonitrile, their association constants, thermodynamic properties and other related properties were studied. Isoniazid (INH), a widely used anti tubercular agent was found to form beautifully colored charge-transfer complexes with p-chloranil, chloranilic acid and tetracyanoethylene in acetonitrile. The absorption maxima of the complexes were 484, 519 and 479 nm, respectively (isoniazid had no absorption, but the acceptors had absorption in these regions). The composition of the complexes were determined to be 1:1 from Job's method of continuous variations depending on the time period of experiments as the stability of some of the complexes (p-chloranil and tetracyanoethylene complexes) was time dependent. Solid complexes formed between isoniazid and the acceptors were isolated but p-chloranil was found to form two different complexes. FTIR spectra of the complexes and the acceptors were measured. FTIR spectra of the complexes showed considerable shift in absorption peaks, changes in intensities of the peaks and formation of the new band (probably due to hydrogen bonding) on complexation. The thermodynamic association constants and other thermodynamic parameters of the complexes were determined spectrophotometrically taking D and A in varying ratios (2:8-8:2) and also in equimolar ratios. The complex formation was found to be spontaneous and associated with negative changes of ΔG(0), ΔH(0) and ΔS(0). The energies hν(CT) of the charge-transfer complexes were compared with the theoretical values of hν(CT) of the complexes obtained from HOMO and LUMO of the donor and the acceptors. Density function theory utilizing different basis sets was used for calculation. hν(CT) (experimental) values of the transition energies of the complexes in acetonitrile differed from hν(CT) (theoretical) values in the gaseous state. I(D)(V) value of isoniazid was calculated. Charge-transfer complexes were assumed to be partial electrovalent compounds with organic dative ions D(+) and A(-) (in the excited state) and attempts had been made to correlate the energy changes for the formation of the complexes with the energy changes for the formation of electrovalent compounds between M(+) and X(-) ions.
authors.affiliation: Central Forensic Science Laboratory, 30 Gorachand Road, Kolkata 700014, West Bengal, India.
authors.forename: Seema
authors.initials: S
authors.lastname: Bagchi Chattaraj
authors.forename: Kakali
authors.initials: K
authors.lastname: Sharma
authors.forename: Ashutosh
authors.initials: A
authors.lastname: Chakrabortty
authors.forename: Sujit Chandra
authors.initials: SC
authors.lastname: Lahiri
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D016227:Benzoquinones / Q000737:chemistry*; D002703:Chloranil / Q000737:chemistry*; D004583:Electrons; D005030:Ethylenes / Q000737:chemistry*; D007538:Isoniazid / Q000737:chemistry*; D007700:Kinetics; D008962:Models, Theoretical; D009570:Nitriles / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013816:Thermodynamics
chemical_list: D000097:Acetonitriles; D016227:Benzoquinones; D005030:Ethylenes; D009570:Nitriles; D002703:Chloranil; C003393:tetracyanoethylene; D007538:Isoniazid; C014400:chloranilic acid; C032159:acetonitrile