Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction

Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction

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(...

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Main Authors: Mark-Lee, Wun Fui, Chong, Yan Yi, Law, Kung Pui, Ishak Ahmad, Mohammad Kassim
Format: Article
Language:English
Published: Penerbit Universiti Kebangsaan Malaysia 2018
Online Access:http://journalarticle.ukm.my/12166/
http://journalarticle.ukm.my/12166/
http://journalarticle.ukm.my/12166/1/17%20Wun%20Fui%20Mark-Lee.pdf
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spelling ukm-121662018-10-10T00:07:46Z http://journalarticle.ukm.my/12166/ 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 Ishak Ahmad, Mohammad Kassim, 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 = 90º and 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. Penerbit Universiti Kebangsaan Malaysia 2018-07 Article PeerReviewed application/pdf en http://journalarticle.ukm.my/12166/1/17%20Wun%20Fui%20Mark-Lee.pdf Mark-Lee, Wun Fui and Chong, Yan Yi and Law, Kung Pui and Ishak Ahmad, and Mohammad Kassim, (2018) Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction. Sains Malaysiana, 47 (7). pp. 1491-1499. ISSN 0126-6039 http://www.ukm.my/jsm/english_journals/vol47num7_2018/contentsVol47num7_2018.html
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language English
description 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 = 90º and 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.
format Article
author Mark-Lee, Wun Fui
Chong, Yan Yi
Law, Kung Pui
Ishak Ahmad,
Mohammad Kassim,
spellingShingle Mark-Lee, Wun Fui
Chong, Yan Yi
Law, Kung Pui
Ishak Ahmad,
Mohammad Kassim,
Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction
author_facet Mark-Lee, Wun Fui
Chong, Yan Yi
Law, Kung Pui
Ishak Ahmad,
Mohammad Kassim,
author_sort Mark-Lee, Wun Fui
title Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction
title_short Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction
title_full Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction
title_fullStr Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction
title_full_unstemmed Synthesis, structure and density functional theory (DFT) study of a rhenium(I) pyridylpyrazol complex as a potential photocatalyst for CO2 reduction
title_sort synthesis, structure and density functional theory (dft) study of a rhenium(i) pyridylpyrazol complex as a potential photocatalyst for co2 reduction
publisher Penerbit Universiti Kebangsaan Malaysia
publishDate 2018
url http://journalarticle.ukm.my/12166/
http://journalarticle.ukm.my/12166/
http://journalarticle.ukm.my/12166/1/17%20Wun%20Fui%20Mark-Lee.pdf
first_indexed 2023-09-18T20:02:00Z
last_indexed 2023-09-18T20:02:00Z
_version_ 1777406910870323200

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