title: Molecular, electronic, and crystal structures of self-assembled hydrothermally synthesized Zn(II)-mercaptonicotinate: a combined spectroscopic and theoretical approach.
abstract: A Zn(II) 2-mercaptonicotinate coordination polymer (Zn1), with Zn(II) ions chelated by both sulfur and oxygen in a distorted square pyramidal environment, and a molecular Zn(II) 2-hydroxynicotinate complex (Zn2) were synthesized by the reaction of zinc acetylacetonate with 2-mercaptonicotinic (Zn1) and 2-hydroxynicotinc (Zn2) acid, respectively, under hydrothermal conditions. The crystal structures of Zn1 and Zn2 were determined by single crystal X-ray diffraction measurements. Dispersion-corrected density functional theory (DFT) calculations reproduce very well the experimental structures and show that Zn1 is stable against hydration, whereas Zn2 is stable against dehydration over wide ranges of temperature and pressure, in agreement with thermogravimetric analysis results. The electronic structure of the two compounds is computed with the DFT+U method. The theoretical valence band agrees well with the X-ray photoelectron spectroscopy experiments. Furthermore, the band gap of Zn1 is found to be narrower than that of Zn1 and is characterized by the presence of sulfur lone pairs at the edge of the valence band.
authors.affiliation: Istituto di Scienze e Tecnologie Molecolari, ISTM-CNR and Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo, 1, I-35131, Padova, Italy.
authors.forename: Maurizio
authors.initials: M
authors.lastname: Casarin
authors.forename: Thomas
authors.initials: T
authors.lastname: Devic
authors.forename: Alessia
authors.initials: A
authors.lastname: Famengo
authors.forename: Daniel
authors.initials: D
authors.lastname: Forrer
authors.forename: Silvia
authors.initials: S
authors.lastname: Gross
authors.forename: Eugenio
authors.initials: E
authors.lastname: Tondello
authors.forename: Andrea
authors.initials: A
authors.lastname: Vittadini
mesh_terms: D003198:Computer Simulation; D018360:Crystallography, X-Ray; D004583:Electrons; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009539:Nicotinic Acids / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D009539:Nicotinic Acids; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; C083470:2-mercaptonicotinic acid; D015032:Zinc