title: Multiple bismuth(III)-thioether secondary interactions integrate metalloporphyrin ligands into functional networks.
abstract: We introduce the 1,2,3-tris(organylthiophenyl) group as a symmetrical, multidentate chelation link for building coordination networks. For this, zinc(II) 5,10,15,20-tetrakis[3',4',5'-tris(methylthio)phenyl]porphyrin was synthesized and integrated into a two-dimensional network via coordination with BiBr3. The coordination link exhibits an unusually complex bonding pattern, involving six S atoms from two neighboring ligands that form multiple Bi-S interactions (distances ranging from 3.08 to 3.63 A) with a dimerlike unit of Bi2Br6. The electronic interaction between the porphyrin center and the Bi2Br6 block was illustrated by the diffuse-reflectance spectrum of the network compound, in which a modest red-shifted feature at 1.8 eV was seen (while the Q-band absorption of the metalloporphyrin core continues to be dominant at 1.9 eV).
authors.affiliation: Department of Chemistry, The George Washington University, 725 21st Street NW, Washington, DC 20052, USA.
authors.forename: Kunhao
authors.initials: K
authors.lastname: Li
authors.forename: Guo
authors.initials: G
authors.lastname: Huang
authors.forename: Zhengtao
authors.initials: Z
authors.lastname: Xu
authors.forename: Mingliang
authors.initials: M
authors.lastname: Zhang
authors.forename: Matthias
authors.initials: M
authors.lastname: Zeller
authors.forename: Allen D
authors.initials: AD
authors.lastname: Hunter
authors.forename: Stephen Sin-Yin
authors.initials: SS
authors.lastname: Chui
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
authors.forename: Wai-Yeung
authors.initials: WY
authors.lastname: Wong
mesh_terms: D001729:Bismuth / Q000737:chemistry*; D008024:Ligands; D046911:Macromolecular Substances / Q000737:chemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D013057:Spectrum Analysis; D013440:Sulfides / Q000737:chemistry*
chemical_list: D008024:Ligands; D046911:Macromolecular Substances; D008665:Metalloporphyrins; D013440:Sulfides; D001729:Bismuth