Synthesis, characterization, and calculated electronic structure of the crystalline metal-organic polymers Hg(SC(6)H(4)S)(en) (n) and Pb(SC(6)H(4)S)(dien) (n)

D L Turner, K H Stone, P W Stephens, Aron Walsh, M P Singh, T P Vaid

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The reaction of Hg(OAc)(2) with 1,4-benzenedithiol in ethylenediamine at 80 degrees C yields [Hg(SC(6)H(4)S)-(en)](n), while the reaction of Pb(OAc)(2) with 1,4-benzenedithiol in diethylenetriamine at 130 degrees C yields [Pb(SC(6)H(4)S)(dien)](n) . Both products are crystalline materials, and structure determination by synchrotron X-ray powder diffraction revealed that both are essentially one-dimensional metal organic polymers with -M-SC(6)H(4)S- repeat units. Diffuse reflectance UV-visible spectroscopy indicates band gaps of 2.89 eV for [Hg(SC(6)H(4)S)(en)](n) and 2.54 eV for [Pb(SC(6)H(4)S)(dien)](n), while density functional theory (DFT) band structure calculations yielded band gaps of 2.24 and 2.10 eV, respectively. The two compounds are both infinite polymers of metal atoms linked by 1,4-benzenedithiolate, the prototypical molecule for single-molecule conductivity studies, yet neither compound has significant electrical conductivity as a pressed pellet. In the case of [Pb(SC(6)H(4)S)(dien)](n) calculations indicate fairly flat bands and therefore low carrier mobilities, while the conduction band of [Hg(SC(6)H(4)S)(en)](n) does have moderate dispersion and a calculated electron effective mass of 0.29.m(e). Hybridization of the empty Hg 6s orbital with SC(6)H(4)S orbitals in the conduction band leads to the band dispersion, and suggests that similar hybrid materials with smaller band gaps will be good semiconductors.
Original languageEnglish
Pages (from-to)370-376
Number of pages7
JournalInorganic Chemistry
Volume51
Issue number1
DOIs
Publication statusPublished - 2 Jan 2012

Fingerprint

Organic polymers
Electronic structure
ethylenediamine
Energy gap
Metals
electronic structure
Crystalline materials
Conduction bands
polymers
synthesis
metals
Molecules
Carrier mobility
Hybrid materials
Synchrotrons
Band structure
X ray powder diffraction
Density functional theory
Polymers
conduction bands

Cite this

Synthesis, characterization, and calculated electronic structure of the crystalline metal-organic polymers Hg(SC(6)H(4)S)(en) (n) and Pb(SC(6)H(4)S)(dien) (n). / Turner, D L; Stone, K H; Stephens, P W; Walsh, Aron; Singh, M P; Vaid, T P.

In: Inorganic Chemistry, Vol. 51, No. 1, 02.01.2012, p. 370-376.

Research output: Contribution to journalArticle

Turner, D L ; Stone, K H ; Stephens, P W ; Walsh, Aron ; Singh, M P ; Vaid, T P. / Synthesis, characterization, and calculated electronic structure of the crystalline metal-organic polymers Hg(SC(6)H(4)S)(en) (n) and Pb(SC(6)H(4)S)(dien) (n). In: Inorganic Chemistry. 2012 ; Vol. 51, No. 1. pp. 370-376.
@article{b0f7bf0b3b7e4fc5ad4afb6a13baecdb,
title = "Synthesis, characterization, and calculated electronic structure of the crystalline metal-organic polymers Hg(SC(6)H(4)S)(en) (n) and Pb(SC(6)H(4)S)(dien) (n)",
abstract = "The reaction of Hg(OAc)(2) with 1,4-benzenedithiol in ethylenediamine at 80 degrees C yields [Hg(SC(6)H(4)S)-(en)](n), while the reaction of Pb(OAc)(2) with 1,4-benzenedithiol in diethylenetriamine at 130 degrees C yields [Pb(SC(6)H(4)S)(dien)](n) . Both products are crystalline materials, and structure determination by synchrotron X-ray powder diffraction revealed that both are essentially one-dimensional metal organic polymers with -M-SC(6)H(4)S- repeat units. Diffuse reflectance UV-visible spectroscopy indicates band gaps of 2.89 eV for [Hg(SC(6)H(4)S)(en)](n) and 2.54 eV for [Pb(SC(6)H(4)S)(dien)](n), while density functional theory (DFT) band structure calculations yielded band gaps of 2.24 and 2.10 eV, respectively. The two compounds are both infinite polymers of metal atoms linked by 1,4-benzenedithiolate, the prototypical molecule for single-molecule conductivity studies, yet neither compound has significant electrical conductivity as a pressed pellet. In the case of [Pb(SC(6)H(4)S)(dien)](n) calculations indicate fairly flat bands and therefore low carrier mobilities, while the conduction band of [Hg(SC(6)H(4)S)(en)](n) does have moderate dispersion and a calculated electron effective mass of 0.29.m(e). Hybridization of the empty Hg 6s orbital with SC(6)H(4)S orbitals in the conduction band leads to the band dispersion, and suggests that similar hybrid materials with smaller band gaps will be good semiconductors.",
author = "Turner, {D L} and Stone, {K H} and Stephens, {P W} and Aron Walsh and Singh, {M P} and Vaid, {T P}",
year = "2012",
month = "1",
day = "2",
doi = "10.1021/ic201779a",
language = "English",
volume = "51",
pages = "370--376",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Synthesis, characterization, and calculated electronic structure of the crystalline metal-organic polymers Hg(SC(6)H(4)S)(en) (n) and Pb(SC(6)H(4)S)(dien) (n)

AU - Turner, D L

AU - Stone, K H

AU - Stephens, P W

AU - Walsh, Aron

AU - Singh, M P

AU - Vaid, T P

PY - 2012/1/2

Y1 - 2012/1/2

N2 - The reaction of Hg(OAc)(2) with 1,4-benzenedithiol in ethylenediamine at 80 degrees C yields [Hg(SC(6)H(4)S)-(en)](n), while the reaction of Pb(OAc)(2) with 1,4-benzenedithiol in diethylenetriamine at 130 degrees C yields [Pb(SC(6)H(4)S)(dien)](n) . Both products are crystalline materials, and structure determination by synchrotron X-ray powder diffraction revealed that both are essentially one-dimensional metal organic polymers with -M-SC(6)H(4)S- repeat units. Diffuse reflectance UV-visible spectroscopy indicates band gaps of 2.89 eV for [Hg(SC(6)H(4)S)(en)](n) and 2.54 eV for [Pb(SC(6)H(4)S)(dien)](n), while density functional theory (DFT) band structure calculations yielded band gaps of 2.24 and 2.10 eV, respectively. The two compounds are both infinite polymers of metal atoms linked by 1,4-benzenedithiolate, the prototypical molecule for single-molecule conductivity studies, yet neither compound has significant electrical conductivity as a pressed pellet. In the case of [Pb(SC(6)H(4)S)(dien)](n) calculations indicate fairly flat bands and therefore low carrier mobilities, while the conduction band of [Hg(SC(6)H(4)S)(en)](n) does have moderate dispersion and a calculated electron effective mass of 0.29.m(e). Hybridization of the empty Hg 6s orbital with SC(6)H(4)S orbitals in the conduction band leads to the band dispersion, and suggests that similar hybrid materials with smaller band gaps will be good semiconductors.

AB - The reaction of Hg(OAc)(2) with 1,4-benzenedithiol in ethylenediamine at 80 degrees C yields [Hg(SC(6)H(4)S)-(en)](n), while the reaction of Pb(OAc)(2) with 1,4-benzenedithiol in diethylenetriamine at 130 degrees C yields [Pb(SC(6)H(4)S)(dien)](n) . Both products are crystalline materials, and structure determination by synchrotron X-ray powder diffraction revealed that both are essentially one-dimensional metal organic polymers with -M-SC(6)H(4)S- repeat units. Diffuse reflectance UV-visible spectroscopy indicates band gaps of 2.89 eV for [Hg(SC(6)H(4)S)(en)](n) and 2.54 eV for [Pb(SC(6)H(4)S)(dien)](n), while density functional theory (DFT) band structure calculations yielded band gaps of 2.24 and 2.10 eV, respectively. The two compounds are both infinite polymers of metal atoms linked by 1,4-benzenedithiolate, the prototypical molecule for single-molecule conductivity studies, yet neither compound has significant electrical conductivity as a pressed pellet. In the case of [Pb(SC(6)H(4)S)(dien)](n) calculations indicate fairly flat bands and therefore low carrier mobilities, while the conduction band of [Hg(SC(6)H(4)S)(en)](n) does have moderate dispersion and a calculated electron effective mass of 0.29.m(e). Hybridization of the empty Hg 6s orbital with SC(6)H(4)S orbitals in the conduction band leads to the band dispersion, and suggests that similar hybrid materials with smaller band gaps will be good semiconductors.

UR - http://www.scopus.com/inward/record.url?scp=84855406739&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1021/ic201779a

U2 - 10.1021/ic201779a

DO - 10.1021/ic201779a

M3 - Article

VL - 51

SP - 370

EP - 376

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 1

ER -