π‐π Interactions, Architecture, and Bandwidths in “Molecular Metals”. A Synthetic and Electronic Structure Study of Monomeric and Cofacially Joined Dimeric Germanium Phthalocyanines

K. A. Doris, E. Ciliberto, I. Fragala, Mark A Ratner, Tobin J Marks

Research output: Contribution to journalArticle

Abstract

Small molecule spectroscopy on M(Pc)(OR)2 and ROM(Pc)OM(Pc)OR molecular fragments (M = Si, Ge; Pc = phthalocyaninato) of the conductive polymer [M(Pcp+)O]n provides a unique probe of the band structure‐forming π‐π interactions. We describe here the synthesis and characterization of the M = Ge monomer and dimer where R = (t‐Bu)Me2Si‐. The lowest energy He I photoelectron spectroscopic feature of the dimer is a doublet with a splitting of 0.19(3) eV. This splitting can be associated with the cofacial HOMO‐HOMO Pc‐Pc interaction and translates into a tight‐binding bandwidth in the polymer of 0.38(6) eV. This result is in good agreement with an experimental bandwidth of 0.48(5) eV obtained from a Drude analysis of the {[Ge(Pc)0]I1.1}n reflectance spectrum and a bandwidth of 0.50 eV derived from theoretical calculations.

Original languageEnglish
Pages (from-to)337-346
Number of pages10
JournalIsrael Journal of Chemistry
Volume27
Issue number4
DOIs
Publication statusPublished - 1986

Fingerprint

Germanium
Electronic structure
Metals
Bandwidth
Dimers
Polymers
ROM
Photoelectrons
Monomers
Spectroscopy
Molecules
phthalocyanine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{1eed43ba84be4b7489c4f388dd54251c,
title = "π‐π Interactions, Architecture, and Bandwidths in “Molecular Metals”. A Synthetic and Electronic Structure Study of Monomeric and Cofacially Joined Dimeric Germanium Phthalocyanines",
abstract = "Small molecule spectroscopy on M(Pc)(OR)2 and ROM(Pc)OM(Pc)OR molecular fragments (M = Si, Ge; Pc = phthalocyaninato) of the conductive polymer [M(Pcp+)O]n provides a unique probe of the band structure‐forming π‐π interactions. We describe here the synthesis and characterization of the M = Ge monomer and dimer where R = (t‐Bu)Me2Si‐. The lowest energy He I photoelectron spectroscopic feature of the dimer is a doublet with a splitting of 0.19(3) eV. This splitting can be associated with the cofacial HOMO‐HOMO Pc‐Pc interaction and translates into a tight‐binding bandwidth in the polymer of 0.38(6) eV. This result is in good agreement with an experimental bandwidth of 0.48(5) eV obtained from a Drude analysis of the {[Ge(Pc)0]I1.1}n reflectance spectrum and a bandwidth of 0.50 eV derived from theoretical calculations.",
author = "Doris, {K. A.} and E. Ciliberto and I. Fragala and Ratner, {Mark A} and Marks, {Tobin J}",
year = "1986",
doi = "10.1002/ijch.198600052",
language = "English",
volume = "27",
pages = "337--346",
journal = "Israel Journal of Chemistry",
issn = "0021-2148",
publisher = "Wiley-VCH Verlag",
number = "4",

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TY - JOUR

T1 - π‐π Interactions, Architecture, and Bandwidths in “Molecular Metals”. A Synthetic and Electronic Structure Study of Monomeric and Cofacially Joined Dimeric Germanium Phthalocyanines

AU - Doris, K. A.

AU - Ciliberto, E.

AU - Fragala, I.

AU - Ratner, Mark A

AU - Marks, Tobin J

PY - 1986

Y1 - 1986

N2 - Small molecule spectroscopy on M(Pc)(OR)2 and ROM(Pc)OM(Pc)OR molecular fragments (M = Si, Ge; Pc = phthalocyaninato) of the conductive polymer [M(Pcp+)O]n provides a unique probe of the band structure‐forming π‐π interactions. We describe here the synthesis and characterization of the M = Ge monomer and dimer where R = (t‐Bu)Me2Si‐. The lowest energy He I photoelectron spectroscopic feature of the dimer is a doublet with a splitting of 0.19(3) eV. This splitting can be associated with the cofacial HOMO‐HOMO Pc‐Pc interaction and translates into a tight‐binding bandwidth in the polymer of 0.38(6) eV. This result is in good agreement with an experimental bandwidth of 0.48(5) eV obtained from a Drude analysis of the {[Ge(Pc)0]I1.1}n reflectance spectrum and a bandwidth of 0.50 eV derived from theoretical calculations.

AB - Small molecule spectroscopy on M(Pc)(OR)2 and ROM(Pc)OM(Pc)OR molecular fragments (M = Si, Ge; Pc = phthalocyaninato) of the conductive polymer [M(Pcp+)O]n provides a unique probe of the band structure‐forming π‐π interactions. We describe here the synthesis and characterization of the M = Ge monomer and dimer where R = (t‐Bu)Me2Si‐. The lowest energy He I photoelectron spectroscopic feature of the dimer is a doublet with a splitting of 0.19(3) eV. This splitting can be associated with the cofacial HOMO‐HOMO Pc‐Pc interaction and translates into a tight‐binding bandwidth in the polymer of 0.38(6) eV. This result is in good agreement with an experimental bandwidth of 0.48(5) eV obtained from a Drude analysis of the {[Ge(Pc)0]I1.1}n reflectance spectrum and a bandwidth of 0.50 eV derived from theoretical calculations.

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U2 - 10.1002/ijch.198600052

DO - 10.1002/ijch.198600052

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VL - 27

SP - 337

EP - 346

JO - Israel Journal of Chemistry

JF - Israel Journal of Chemistry

SN - 0021-2148

IS - 4

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