Abstract
The Re(I) complex, [Re(PyPzH)(CO)3Cl] where PyPzH = 2-(1H-pyrazol-3-yl)pyridine, was successfully synthesised and characterised with an infrared (IR), ultraviolet-visible (UV-Vis), 1H and 13C nuclear magnetic resonance (NMR) spectroscopies and X-ray crystallography. The IR spectrum featured three n(C≡O), n(N-H), n(C=N) and n(C=C) signals at (1860-2020), 3137, 1614 and 1513 cm-1, respectively. The UV-Vis spectrum of the complex exhibited ligand-centred (π®>*) electronic excitations [λmax = 227 nm, ε = 1.942 x 104 M-1cm-1; lmax = 292 nm, ε = 0.853 x 104 M-1cm-1] and a metal-to-ligand charge transfer (MLCT) band [lmax = 331 nm, ε = 0.467 x 104 M-1cm-1]. The 13C and 1H-NMR spectra exhibited the characteristic signals of the three C≡O (189.0 – 199.0 ppm) and NH (14.84 ppm), respectively. The X-ray structure of [Re(PyPzH)(CO)3Cl] showed the crystal adopted a monoclinic system with a C2/c space group [unit cell dimensions: a = 27.7422(14) Å, b = 11.1456(5) Å, c = 9.2461(4) Å with α = γ = 90ºand β = 92.552(2)º]. Density functional theory (DFT) and time-dependent (TD) DFT calculations were performed to investigate the optimised structural geometry and electronic properties of the title complex. The results showed that the highest-occupied molecular orbital (HOMO) was predominantly found on the dπ-orbitals of Re(I), Cl and CO. While the lowest-unoccupied molecular orbital (LUMO) was located on the PyPzH moiety. The structural and photophysical properties of the [Re(PyPzH)(CO)3Cl] were established and the reaction enthalpies for the dissociation of Cl atom in the formation of [Re(PyPzH)(CO)3]• were discussed in view of its potential application for photocatalytic CO2 reduction.
| Original language | English |
|---|---|
| Pages (from-to) | 1491-1499 |
| Number of pages | 9 |
| Journal | Sains Malaysiana |
| Volume | 47 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - 1 Jul 2018 |
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Keywords
- Crystal structure
- DFT
- Photocatalytic CO2 reduction
- Pyridylpyrazole
- Rhenium(I) polypyridine
ASJC Scopus subject areas
- General
Cite this
Synthesis, structure and density functional theory (DFT) study of a Rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction. / Mark-Lee, Wun Fui; Chong, Yan Yi; Law, Kung Pui; Ahmad, Ishak; Kassim, Mohammad.
In: Sains Malaysiana, Vol. 47, No. 7, 01.07.2018, p. 1491-1499.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Synthesis, structure and density functional theory (DFT) study of a Rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction
AU - Mark-Lee, Wun Fui
AU - Chong, Yan Yi
AU - Law, Kung Pui
AU - Ahmad, Ishak
AU - Kassim, Mohammad
PY - 2018/7/1
Y1 - 2018/7/1
N2 - The Re(I) complex, [Re(PyPzH)(CO)3Cl] where PyPzH = 2-(1H-pyrazol-3-yl)pyridine, was successfully synthesised and characterised with an infrared (IR), ultraviolet-visible (UV-Vis), 1H and 13C nuclear magnetic resonance (NMR) spectroscopies and X-ray crystallography. The IR spectrum featured three n(C≡O), n(N-H), n(C=N) and n(C=C) signals at (1860-2020), 3137, 1614 and 1513 cm-1, respectively. The UV-Vis spectrum of the complex exhibited ligand-centred (π®>*) electronic excitations [λmax = 227 nm, ε = 1.942 x 104 M-1cm-1; lmax = 292 nm, ε = 0.853 x 104 M-1cm-1] and a metal-to-ligand charge transfer (MLCT) band [lmax = 331 nm, ε = 0.467 x 104 M-1cm-1]. The 13C and 1H-NMR spectra exhibited the characteristic signals of the three C≡O (189.0 – 199.0 ppm) and NH (14.84 ppm), respectively. The X-ray structure of [Re(PyPzH)(CO)3Cl] showed the crystal adopted a monoclinic system with a C2/c space group [unit cell dimensions: a = 27.7422(14) Å, b = 11.1456(5) Å, c = 9.2461(4) Å with α = γ = 90ºand β = 92.552(2)º]. Density functional theory (DFT) and time-dependent (TD) DFT calculations were performed to investigate the optimised structural geometry and electronic properties of the title complex. The results showed that the highest-occupied molecular orbital (HOMO) was predominantly found on the dπ-orbitals of Re(I), Cl and CO. While the lowest-unoccupied molecular orbital (LUMO) was located on the PyPzH moiety. The structural and photophysical properties of the [Re(PyPzH)(CO)3Cl] were established and the reaction enthalpies for the dissociation of Cl atom in the formation of [Re(PyPzH)(CO)3]• were discussed in view of its potential application for photocatalytic CO2 reduction.
AB - The Re(I) complex, [Re(PyPzH)(CO)3Cl] where PyPzH = 2-(1H-pyrazol-3-yl)pyridine, was successfully synthesised and characterised with an infrared (IR), ultraviolet-visible (UV-Vis), 1H and 13C nuclear magnetic resonance (NMR) spectroscopies and X-ray crystallography. The IR spectrum featured three n(C≡O), n(N-H), n(C=N) and n(C=C) signals at (1860-2020), 3137, 1614 and 1513 cm-1, respectively. The UV-Vis spectrum of the complex exhibited ligand-centred (π®>*) electronic excitations [λmax = 227 nm, ε = 1.942 x 104 M-1cm-1; lmax = 292 nm, ε = 0.853 x 104 M-1cm-1] and a metal-to-ligand charge transfer (MLCT) band [lmax = 331 nm, ε = 0.467 x 104 M-1cm-1]. The 13C and 1H-NMR spectra exhibited the characteristic signals of the three C≡O (189.0 – 199.0 ppm) and NH (14.84 ppm), respectively. The X-ray structure of [Re(PyPzH)(CO)3Cl] showed the crystal adopted a monoclinic system with a C2/c space group [unit cell dimensions: a = 27.7422(14) Å, b = 11.1456(5) Å, c = 9.2461(4) Å with α = γ = 90ºand β = 92.552(2)º]. Density functional theory (DFT) and time-dependent (TD) DFT calculations were performed to investigate the optimised structural geometry and electronic properties of the title complex. The results showed that the highest-occupied molecular orbital (HOMO) was predominantly found on the dπ-orbitals of Re(I), Cl and CO. While the lowest-unoccupied molecular orbital (LUMO) was located on the PyPzH moiety. The structural and photophysical properties of the [Re(PyPzH)(CO)3Cl] were established and the reaction enthalpies for the dissociation of Cl atom in the formation of [Re(PyPzH)(CO)3]• were discussed in view of its potential application for photocatalytic CO2 reduction.
KW - Crystal structure
KW - DFT
KW - Photocatalytic CO2 reduction
KW - Pyridylpyrazole
KW - Rhenium(I) polypyridine
UR - http://www.scopus.com/inward/record.url?scp=85051841661&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85051841661&partnerID=8YFLogxK
U2 - 10.17576/jsm-2018-4707-17
DO - 10.17576/jsm-2018-4707-17
M3 - Article
AN - SCOPUS:85051841661
VL - 47
SP - 1491
EP - 1499
JO - Sains Malaysiana
JF - Sains Malaysiana
SN - 0126-6039
IS - 7
ER -