Synthesis and Characterization of Bis(2,2'-bipyridyl)Platinum(I): A Novel Microtubular Linear-Chain Complex

Roger Palmans; D. Brent MacQueen; Cortlandt G. Pierpont; Arthur J. Frank

doi:10.1021/ja962491m

Synthesis and Characterization of Bis(2,2'-bipyridyl)Platinum(I): A Novel Microtubular Linear-Chain Complex

Roger Palmans, D. Brent MacQueen, Cortlandt G. Pierpont, Arthur J. Frank

Chemistry and Nanoscience

Research output: Contribution to journal › Article › peer-review

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Abstract

One-electron reduction of [Pt(bpy)₂]²⁺ (bpy = 2,2′-bipyridyl) in aqueous solution results in the formation of black-green 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^I complex with a d⁹ electronic configuration and with the composition [Pt(bpy)₂]NO₃·2H₂O. X-ray crystallographic analysis shows that the crystalline needles consist of linear chains of discrete [Pt^I(bpy)₂] units with a Pt-Pt distance of 3.563(1) Å and with each bipyridyl ligand overlapping face-to-face (eclipsed) with its nearest neighbor. At the monomeric level, the structure of [Pt^I(bpy)₂] units exhibits a distorted square-planar configuration with structural parameters very similar to those of the parent Pt^II complex, [Pt(bpy)₂](NO₃)₂·H₂O. 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. Because of extensive solid-state interactions between stacked monomeric [Pt^I(bpy)₂] units, the crystals absorb strongly over the whole visible region and far into the near infrared. Their room temperature electrical conductivity is relatively high, 10 Ω^-1 cm^-1.

Original language	American English
Pages (from-to)	12647-12653
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	118
Issue number	50
DOIs	https://doi.org/10.1021/ja962491m https://doi.org/10.1021/ja962491m
State	Published - 18 Dec 1996

NREL Publication Number

NREL/JA-452-20015

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@article{96c052594c004ac9b559e7ab70ff0618,

title = "Synthesis and Characterization of Bis(2,2'-bipyridyl)Platinum(I): A Novel Microtubular Linear-Chain Complex",

abstract = "One-electron reduction of [Pt(bpy)2]2+ (bpy = 2,2′-bipyridyl) in aqueous solution results in the formation of black-green 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 PtI complex with a d9 electronic configuration and with the composition [Pt(bpy)2]NO3·2H2O. X-ray crystallographic analysis shows that the crystalline needles consist of linear chains of discrete [PtI(bpy)2] units with a Pt-Pt distance of 3.563(1) {\AA} and with each bipyridyl ligand overlapping face-to-face (eclipsed) with its nearest neighbor. At the monomeric level, the structure of [PtI(bpy)2] units exhibits a distorted square-planar configuration with structural parameters very similar to those of the parent PtII complex, [Pt(bpy)2](NO3)2·H2O. 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. Because of extensive solid-state interactions between stacked monomeric [PtI(bpy)2] units, the crystals absorb strongly over the whole visible region and far into the near infrared. Their room temperature electrical conductivity is relatively high, 10 Ω-1 cm-1.",

author = "Roger Palmans and MacQueen, {D. Brent} and Pierpont, {Cortlandt G.} and Frank, {Arthur J.}",

year = "1996",

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T1 - Synthesis and Characterization of Bis(2,2'-bipyridyl)Platinum(I): A Novel Microtubular Linear-Chain Complex

AU - Palmans, Roger

AU - MacQueen, D. Brent

AU - Pierpont, Cortlandt G.

AU - Frank, Arthur J.

PY - 1996/12/18

Y1 - 1996/12/18

N2 - One-electron reduction of [Pt(bpy)2]2+ (bpy = 2,2′-bipyridyl) in aqueous solution results in the formation of black-green 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 PtI complex with a d9 electronic configuration and with the composition [Pt(bpy)2]NO3·2H2O. X-ray crystallographic analysis shows that the crystalline needles consist of linear chains of discrete [PtI(bpy)2] units with a Pt-Pt distance of 3.563(1) Å and with each bipyridyl ligand overlapping face-to-face (eclipsed) with its nearest neighbor. At the monomeric level, the structure of [PtI(bpy)2] units exhibits a distorted square-planar configuration with structural parameters very similar to those of the parent PtII complex, [Pt(bpy)2](NO3)2·H2O. 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. Because of extensive solid-state interactions between stacked monomeric [PtI(bpy)2] units, the crystals absorb strongly over the whole visible region and far into the near infrared. Their room temperature electrical conductivity is relatively high, 10 Ω-1 cm-1.

AB - One-electron reduction of [Pt(bpy)2]2+ (bpy = 2,2′-bipyridyl) in aqueous solution results in the formation of black-green 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 PtI complex with a d9 electronic configuration and with the composition [Pt(bpy)2]NO3·2H2O. X-ray crystallographic analysis shows that the crystalline needles consist of linear chains of discrete [PtI(bpy)2] units with a Pt-Pt distance of 3.563(1) Å and with each bipyridyl ligand overlapping face-to-face (eclipsed) with its nearest neighbor. At the monomeric level, the structure of [PtI(bpy)2] units exhibits a distorted square-planar configuration with structural parameters very similar to those of the parent PtII complex, [Pt(bpy)2](NO3)2·H2O. 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. Because of extensive solid-state interactions between stacked monomeric [PtI(bpy)2] units, the crystals absorb strongly over the whole visible region and far into the near infrared. Their room temperature electrical conductivity is relatively high, 10 Ω-1 cm-1.

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ER -

Synthesis and Characterization of Bis(2,2'-bipyridyl)Platinum(I): A Novel Microtubular Linear-Chain Complex

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