title: TDDFT studies on electronic structures, chiroptical properties and solvent effect on the CD spectra of diphosphonate-functionalized polyoxomolybdates.
abstract: The ultraviolet-visible and electronic circular dichroism (UV-vis/ECD) spectra of diphosphonate-functionalized asymmetric cantilever-type chiral polyoxomolybdate (POM) enantiomer R-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-) (R) were systematically investigated using time-dependent density functional theory (TDDFT) method. From the view of molecular structure and relative energy, we inferred that there is likely a structural conversion from enantiomers R to S-{Mo2O5[(Mo2O6)NH3CH2CH2CH2C(O)(PO3)2]2}(6-) (S) via the intermediate configuration (IN). The ECD spectra of the enantiomer R were produced over the range of 3.0-6.3eV. The UV-vis and ECD spectra of enantiomer R in the gas phase and different solvents were calculated. The results reveal that the UV-vis and ECD spectra of the chiral POM in gas phase, polar solvent, or non-polar solvent are different. The calculated electron density difference maps (EDDMs) display that the POM cluster is a chiroptical chromophore in studied compound.
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Ren Min Street No. 5268, Changchun, Jilin 130024, PR China.
authors.forename: Yuan-Mei
authors.initials: YM
authors.lastname: Sang
authors.forename: Li-Kai
authors.initials: LK
authors.lastname: Yan
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Wang
authors.forename: Na-Na
authors.initials: NN
authors.lastname: Ma
authors.forename: Zhong-Min
authors.initials: ZM
authors.lastname: Su
mesh_terms: D002942:Circular Dichroism; D004164:Diphosphonates / Q000737:chemistry*; D004583:Electrons; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D000071228:Polyelectrolytes; D011108:Polymers / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*
chemical_list: D004164:Diphosphonates; D008982:Molybdenum; D000071228:Polyelectrolytes; D011108:Polymers; D012997:Solvents; C044659:molybdate
keywords: Charge transfer; Chirality; ECD spectra; Polyoxometalate