Abstract
A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5- dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2- hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten with the molecular formula of C54H54O12S 6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a = 12.756(2) Å, b = 21.560(3) Å, c = 24.980(4) Å and β = 103.998(3). Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.
| Original language | English |
|---|---|
| Pages (from-to) | 208-215 |
| Number of pages | 8 |
| Journal | Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy |
| Volume | 120 |
| DOIs | |
| Publication status | Published - 2014 |
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Keywords
- DFT
- Dithiolene
- Homoleptic
- Non-innocent
- Tungsten
ASJC Scopus subject areas
- Instrumentation
- Atomic and Molecular Physics, and Optics
- Analytical Chemistry
- Spectroscopy
Cite this
Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten. / Khuzaimah, Arifin; Effery Minggu, Lorna; Wan Daud, Wan Ramli; Mohd. Yamin, Bohari; Daik, Rusli; Kassim, Mohammad.
In: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, Vol. 120, 2014, p. 208-215.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten
AU - Khuzaimah, Arifin
AU - Effery Minggu, Lorna
AU - Wan Daud, Wan Ramli
AU - Mohd. Yamin, Bohari
AU - Daik, Rusli
AU - Kassim, Mohammad
PY - 2014
Y1 - 2014
N2 - A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5- dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2- hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten with the molecular formula of C54H54O12S 6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a = 12.756(2) Å, b = 21.560(3) Å, c = 24.980(4) Å and β = 103.998(3). Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.
AB - A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5- dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2- hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten with the molecular formula of C54H54O12S 6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a = 12.756(2) Å, b = 21.560(3) Å, c = 24.980(4) Å and β = 103.998(3). Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.
KW - DFT
KW - Dithiolene
KW - Homoleptic
KW - Non-innocent
KW - Tungsten
UR - http://www.scopus.com/inward/record.url?scp=84886732846&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84886732846&partnerID=8YFLogxK
U2 - 10.1016/j.saa.2013.09.069
DO - 10.1016/j.saa.2013.09.069
M3 - Article
VL - 120
SP - 208
EP - 215
JO - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
JF - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
SN - 1386-1425
ER -