title: Theoretical understanding of ruthenium(II) based fluoride sensor derived from 4,5-bis(benzimidazol-2-yl)imidazole (H3ImBzim) and bipyridine: electronic structure and binding nature.
abstract: Using density functional theory (DFT) approach, we assessed the newly developed fluoride sensor: [(bpy)(2)Ru(H(3)ImBzim)](2+) (denoted as 1, where H(3)ImBzim = 4,5-bis(benzimidazol-2-yl)imidazole and byp = 2,2'-bipyridine). On the basis of our benchmark test, a PBE0 functional with a LanL2DZ basis set was chosen to explore the electronic structure of 1 in both ground and singlet excited states in acetonitrile solution. Both absorption bands at 426 and 352 nm are assigned as metal-to-ligand charge-transfer transition characters. By analyzing the difference of absorption spectrum between the binding adducts and the experimental measurement, the fluoride detection process was found to be driven by the proton transfer model, which makes 1 not only capable of detecting fluoride, but also for other Bønster base anions. And the result is in general accordance with the experimental observations. We hope the current exploration can give some knowledge about the detection mechanism of the F(-) anion sensor and provide some inspiration for the design of functional molecular detectors for F(-) anion.
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China, and.
authors.forename: Jian
authors.initials: J
authors.lastname: Wang
authors.forename: Fu-Quan
authors.initials: FQ
authors.lastname: Bai
authors.forename: Bao-Hui
authors.initials: BH
authors.lastname: Xia
authors.forename: Lei
authors.initials: L
authors.lastname: Sun
authors.forename: Hong-Xing
authors.initials: HX
authors.lastname: Zhang
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry*; D001562:Benzimidazoles / Q000737:chemistry*; D002623:Chemistry Techniques, Analytical / Q000295:instrumentation*; D003124:Colorimetry; D004583:Electrons; D005459:Fluorides / Q000032:analysis*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D011522:Protons; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: C558818:4,5-bis(benzimidazol-2-yl)imidazole; D001562:Benzimidazoles; D011522:Protons; D015082:2,2'-Dipyridyl; D012428:Ruthenium; D005459:Fluorides