Trimethyltetrathiafulvalene bearing an N-methylpyridinium substituent: Synthesis, crystal structures, and charge transfer properties

Adrian J. Moore; Andrei S. Batsanov; Martin R. Bryce; Judith A.K. Howard; Vladimir Khodorkovsky; Lev Shapiro; Alex Shames

doi:10.1002/1099-0690(200101)2001:1<73::AID-EJOC73>3.0.CO;2-0

Trimethyltetrathiafulvalene bearing an N-methylpyridinium substituent: Synthesis, crystal structures, and charge transfer properties

Adrian J. Moore, Andrei S. Batsanov, Martin R. Bryce, Judith A.K. Howard, Vladimir Khodorkovsky, Lev Shapiro, Alex Shames

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

31 Scopus citations

Abstract

The synthesis of 4,4′,5-trimethyl-5′-(4-pyridyl)tetrathiafulvalene (3), has been accomplished by reaction of the stannylated precursor 2 with 4-bromopyridine. Alkylation of 3 affords the N-methylpyridinium salt 4 which displays intramolecular charge transfer properties in solution as deduced from UV/Vis spectra, cyclic voltammetric data, and semiempirical quantum mechanical calculations. The X-ray crystal structures of neutral molecule 3, the salt (4⁺)I^- and the charge transfer salt (4⁺)₂(TCNQ₃)^2-. are reported. The positive charge in (4⁺)I^- and (4⁺)₂(TCNQ₃)^2-. is predominantly confined on the pyridinium ring. The structure of (4⁺)₂(TCNQ₃)^2-. comprises segregated stacks of cations and TCNQ radical anions, with the anions overlapping in the usual ring-over-bond fashion. This salt is a semiconductor (σ_rt= 10^-2 S cm^-1).

Original language	English
Pages (from-to)	73-78
Number of pages	6
Journal	European Journal of Organic Chemistry
Issue number	1
DOIs	https://doi.org/10.1002/1099-0690(200101)2001:1<73::AID-EJOC73>3.0.CO;2-0
State	Published - 1 Jan 2001

Keywords

Charge-transfer
Crystal structures
Electron donors
Tetracyano-p-quinodimethane
Tetrathiafulvalenes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry

Access to Document

10.1002/1099-0690(200101)2001:1<73::AID-EJOC73>3.0.CO;2-0

Cite this

Moore, A. J., Batsanov, A. S., Bryce, M. R., Howard, J. A. K., Khodorkovsky, V., Shapiro, L., & Shames, A. (2001). Trimethyltetrathiafulvalene bearing an N-methylpyridinium substituent: Synthesis, crystal structures, and charge transfer properties. European Journal of Organic Chemistry, (1), 73-78. https://doi.org/10.1002/1099-0690(200101)2001:1<73::AID-EJOC73>3.0.CO;2-0

@article{7917db02b4364a03bdf5fbbe4428d204,

title = "Trimethyltetrathiafulvalene bearing an N-methylpyridinium substituent: Synthesis, crystal structures, and charge transfer properties",

abstract = "The synthesis of 4,4′,5-trimethyl-5′-(4-pyridyl)tetrathiafulvalene (3), has been accomplished by reaction of the stannylated precursor 2 with 4-bromopyridine. Alkylation of 3 affords the N-methylpyridinium salt 4 which displays intramolecular charge transfer properties in solution as deduced from UV/Vis spectra, cyclic voltammetric data, and semiempirical quantum mechanical calculations. The X-ray crystal structures of neutral molecule 3, the salt (4+)I- and the charge transfer salt (4+)2(TCNQ3)2-. are reported. The positive charge in (4+)I- and (4+)2(TCNQ3)2-. is predominantly confined on the pyridinium ring. The structure of (4+)2(TCNQ3)2-. comprises segregated stacks of cations and TCNQ radical anions, with the anions overlapping in the usual ring-over-bond fashion. This salt is a semiconductor (σrt= 10-2 S cm-1).",

keywords = "Charge-transfer, Crystal structures, Electron donors, Tetracyano-p-quinodimethane, Tetrathiafulvalenes",

author = "Moore, {Adrian J.} and Batsanov, {Andrei S.} and Bryce, {Martin R.} and Howard, {Judith A.K.} and Vladimir Khodorkovsky and Lev Shapiro and Alex Shames",

year = "2001",

month = jan,

day = "1",

doi = "10.1002/1099-0690(200101)2001:1<73::AID-EJOC73>3.0.CO;2-0",

language = "English",

pages = "73--78",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "John Wiley and Sons Ltd",

number = "1",

}

TY - JOUR

T1 - Trimethyltetrathiafulvalene bearing an N-methylpyridinium substituent

T2 - Synthesis, crystal structures, and charge transfer properties

AU - Moore, Adrian J.

AU - Batsanov, Andrei S.

AU - Bryce, Martin R.

AU - Howard, Judith A.K.

AU - Khodorkovsky, Vladimir

AU - Shapiro, Lev

AU - Shames, Alex

PY - 2001/1/1

Y1 - 2001/1/1

N2 - The synthesis of 4,4′,5-trimethyl-5′-(4-pyridyl)tetrathiafulvalene (3), has been accomplished by reaction of the stannylated precursor 2 with 4-bromopyridine. Alkylation of 3 affords the N-methylpyridinium salt 4 which displays intramolecular charge transfer properties in solution as deduced from UV/Vis spectra, cyclic voltammetric data, and semiempirical quantum mechanical calculations. The X-ray crystal structures of neutral molecule 3, the salt (4+)I- and the charge transfer salt (4+)2(TCNQ3)2-. are reported. The positive charge in (4+)I- and (4+)2(TCNQ3)2-. is predominantly confined on the pyridinium ring. The structure of (4+)2(TCNQ3)2-. comprises segregated stacks of cations and TCNQ radical anions, with the anions overlapping in the usual ring-over-bond fashion. This salt is a semiconductor (σrt= 10-2 S cm-1).

AB - The synthesis of 4,4′,5-trimethyl-5′-(4-pyridyl)tetrathiafulvalene (3), has been accomplished by reaction of the stannylated precursor 2 with 4-bromopyridine. Alkylation of 3 affords the N-methylpyridinium salt 4 which displays intramolecular charge transfer properties in solution as deduced from UV/Vis spectra, cyclic voltammetric data, and semiempirical quantum mechanical calculations. The X-ray crystal structures of neutral molecule 3, the salt (4+)I- and the charge transfer salt (4+)2(TCNQ3)2-. are reported. The positive charge in (4+)I- and (4+)2(TCNQ3)2-. is predominantly confined on the pyridinium ring. The structure of (4+)2(TCNQ3)2-. comprises segregated stacks of cations and TCNQ radical anions, with the anions overlapping in the usual ring-over-bond fashion. This salt is a semiconductor (σrt= 10-2 S cm-1).

KW - Charge-transfer

KW - Crystal structures

KW - Electron donors

KW - Tetracyano-p-quinodimethane

KW - Tetrathiafulvalenes

UR - http://www.scopus.com/inward/record.url?scp=0035133187&partnerID=8YFLogxK

U2 - 10.1002/1099-0690(200101)2001:1<73::AID-EJOC73>3.0.CO;2-0

DO - 10.1002/1099-0690(200101)2001:1<73::AID-EJOC73>3.0.CO;2-0

M3 - Article

AN - SCOPUS:0035133187

SN - 1434-193X

SP - 73

EP - 78

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 1

ER -

Trimethyltetrathiafulvalene bearing an N-methylpyridinium substituent: Synthesis, crystal structures, and charge transfer properties

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this