title: Halogen vs hydrogen bonding in thiazoline-2-thione stabilization with σ- and π-electron acceptors adducts: theoretical and experimental study.
abstract: Molecular charge-transfer complexes (CT) between thiazoline-2-thione (THZ) and different σ- (I2) and π-acceptors (Tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL)) were investigated. UV-Vis absorption spectroscopy and theoretical calculations using both MP2/aug-cc-pVDZ-PP and B3LYP/6-311++G(d,p) level of theory were corroborated to study the nature of the stabilizing forces for THZ-I2, THZ-DDQ, THZ-TCNE, and THZ-CHL. Halogen bonding (XB) was the stabilizing attractive force in THZ-I2 and THZ-CHL whereas; hydrogen bonding (HB) was dominated in both THZ-TCNE, and THZ-DDQ complexes. Formation constant (K), extinction coefficient (ɛ), thermodynamic parameters such as enthalpy change (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) were measured in different solvents.
authors.affiliation: Biotechnology and Fish Processing Department, Faculty of Aquatic and Fisheries Sciences, Kafrelsheikh University, 33516 Kafr ElSheikh, Egypt; Nanochemistry Laboratory, Chemistry Department, Faculty of Science, Kafrelsheikh University, 33516 Kafr ElSheikh, Egypt. Electronic address: h.elsheshtawy@fsh.kfs.edu.eg.
authors.forename: Hamdy S
authors.initials: HS
authors.lastname: El-Sheshtawy
authors.affiliation: Chemistry Department, Faculty of Science, South Valley University, Qena 83523, Egypt.
authors.forename: Hassan M A
authors.initials: HM
authors.lastname: Salman
authors.affiliation: Nanochemistry Laboratory, Chemistry Department, Faculty of Science, Kafrelsheikh University, 33516 Kafr ElSheikh, Egypt.
authors.forename: Maged
authors.initials: M
authors.lastname: El-Kemary
mesh_terms: D016227:Benzoquinones / Q000737:chemistry; D002703:Chloranil / Q000737:chemistry; D004583:Electrons; D005030:Ethylenes / Q000737:chemistry; D006219:Halogens / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics; D053778:Thiazolidines / Q000737:chemistry*
chemical_list: D016227:Benzoquinones; D005030:Ethylenes; D006219:Halogens; D009570:Nitriles; D012997:Solvents; D053778:Thiazolidines; D002703:Chloranil; C000928:dichlorodicyanobenzoquinone; C033089:thiazoline-2-thione; C003393:tetracyanoethylene
keywords: Halogen bond; Hydrogen bond; Solvent effect; Thiazoline-2-thione