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Title: Synthesis and characterization of bis(2-2`-bipyridyl)platinum(I): A novel microtubular linear-chain complex

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja962491m· OSTI ID:437742
; ;  [1];  [2]
  1. National Renewable Energy Lab., Golden, CO (United States)
  2. Univ. of Colorado, Boulder, CO (United States)

One-electron reduction of [Pt(bpy){sub 2}]{sup 2+} (bpy = 2,2`-bipyridyl) in aqueous solution results in the formation of black-greeen lustrous needles on solid electrodes. The crystalline needles grow perpendicularly from the substrate surface and reach lengths of 1-2 cm. Elemental analysis, X-ray photoelectron spectroscopy, and electrochemical measurements indicate that the new compound is a genuine Pt{sup I} complex with a d{sup 9} electronic configuration and with the composition [Pt(bpy){sub 2}]NO{sub 3}.2H{sub 2}O. X-ray crystallographic analysis shows that the crystalline needles consist of linear chains of discrete [Pt{sup I}(bpy){sub 2}] units with a Pt-Pt distance of 3.563 (1) A and with each bipyridyl ligand overlapping face-to-face (eclipsed) with its nearest neighbor. At the monomeric level, the structure of [Pt{sup I}(bpy){sub 2}] units exhibits a distorted square-planar configuration with structural parameters very similar to those of the parent Pt{sup II} complex, [Pt(bpy){sub 2}](NO{sub 3}){sub 2}.H{sub 2}O. The new linear-chain compound was prepared by chemical and electrochemical methods. The resulting crystals are relatively stable in air but oxidize slowly over a period of weeks. Scanning electron microscopy reveals that the crystals are tubular with a hollow near-hexagonal morphology. Cooperative effects influence the optical and electrical properties of the crystals. 54 refs., 6 figs., 3 tabs.

OSTI ID:
437742
Journal Information:
Journal of the American Chemical Society, Vol. 118, Issue 50; Other Information: PBD: 18 Dec 1996
Country of Publication:
United States
Language:
English