title: Orientational dynamics of a charge transfer complex in cyclodextrin cavity as receptor.
abstract: This paper reports the structure and dynamics of a twisted intermolecular charge transfer molecule 2-(4-(dimethylamino) styryl)-1-methylpyridinium iodide (o-DASPMI) included inside alpha-, beta- and gamma-cyclodextrin, investigated by using steady state and time-resolved emission spectroscopy and also theoretical modeling. A nice 1 : 1 inclusion complex with beta-CD in the excited state could be found with the dimethylamino group of the molecule sticking out as revealed from steady state and time-resolved emission. The inclusion complex has a longer decay time compared to that in neat water. Time-resolved anisotropy decay has been used to study the rotational dynamics of the molecule inside cyclodextrin cavity. The average angular structure of the inclusion complex as found from semiempirical PM3 calculations corroborates excellently the experimental results of angular orientation in beta-CD. The minimum energy of the complex is found to be nearly 5 A in the length of the molecule with the dimethylamino part sticking out in the bulk water. Hydrogen bonding at the rim hinders the inclusion complex of o-DASPMI in gamma-CD and instead it produces association at the rim. Hydrogen bond breaker urea breaks the bonding of o-DASPMI with the rim of gamma-CD and the formation of inclusion complex with gamma-CD ensues.
authors.affiliation: Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, India.
authors.forename: D
authors.initials: D
authors.lastname: Sahoo
authors.forename: S
authors.initials: S
authors.lastname: Chakravorti
mesh_terms: D002942:Circular Dichroism; D003505:Cyclodextrins / Q000737:chemistry* / Q000378:metabolism*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010777:Photochemistry; D011726:Pyridinium Compounds / Q000737:chemistry / Q000378:metabolism; D013050:Spectrometry, Fluorescence
chemical_list: D003505:Cyclodextrins; D011726:Pyridinium Compounds; C011786:2-(4-(dimethylamino)styryl)-1-methylpyridinium