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Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring

Hartree Fock (HF) and density functional theory (DFT) methods based on a 3-21G set level were used to computationally assess the nonlinear optic (NLO) response of six ruthenium (Ru) arylalkynyl complexes. The low basis set of 3-21G was proved to provide adequate results with difference of only about...

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Main Authors: Abdul Razak, Fazira Ilyana, Abdul Wahab, Roswanira, Jamaludin, Rosmawati, Adamu, Aliyu
Format: Article
Language:English
Published: Penerbit UTM Press 2020
Subjects:
QD Chemistry
Online Access:http://eprints.utm.my/id/eprint/90955/1/FaziraIlyanaAbdul2020_TuningofNonlinearOpticResponseProperties.pdf
http://eprints.utm.my/id/eprint/90955/
http://dx.doi.org/10.11113/mjfas.v16n4.1682
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spelling my.utm.909552021-05-31T13:41:15Z http://eprints.utm.my/id/eprint/90955/ Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring Abdul Razak, Fazira Ilyana Abdul Wahab, Roswanira Jamaludin, Rosmawati Adamu, Aliyu QD Chemistry Hartree Fock (HF) and density functional theory (DFT) methods based on a 3-21G set level were used to computationally assess the nonlinear optic (NLO) response of six ruthenium (Ru) arylalkynyl complexes. The low basis set of 3-21G was proved to provide adequate results with difference of only about 3% between calculation and experimental data. Substitution of Ru-phenyl with six simplified models of Ru-H and Ru-methyl complexes revealed that DFT-based calculations were more accurate than HF in estimating the NLO response. The calculated bond lengths and angles of Ru-methyl were in good agreement with Ru-phenyl. Given that the calculated C≡C stretching vibration and UV-vis maximum absorption for Ru-methyl was comparable to Ru-phenyl, with values corresponding to 2154.56 cm-1 and 460.93 nm, respectively. It was evident that Ru-H, Ru-methyl and Ru-phenyl complexes undergo intraligands π-π* and Laporte forbidden metal d-d transition. Henceforth, it is affirmed that calculations using simplified Ru-H complexes were as much as reliable as the full structure of Ru to assess the NLO response. Assessment of electron inductive effect on Ru-carbonyl (Ru-Co), Ru-cyclopentadienyl (Ru-Cp) and Ru- bipyridine (Ru-bpy) complexes revealed two absorption maxima that appeared in regions 320−375 nm and 382−460 nm, which represent an intraligand π-π* orbital and Laporte forbidden d-d-transition, respectively. Migration of electrons from Ru center to the bipyridine ligand suggests a greater electron acceptor effect than Ru center to the arylalkynyl group. However, Ru conjugated to an electron withdrawing group i.e. carbonyl tend to render lower NLO response while elevating HOMO - LUMO energy gap and Ru to Cα bond lengths. Penerbit UTM Press 2020-07 Article PeerReviewed application/pdf en http://eprints.utm.my/id/eprint/90955/1/FaziraIlyanaAbdul2020_TuningofNonlinearOpticResponseProperties.pdf Abdul Razak, Fazira Ilyana and Abdul Wahab, Roswanira and Jamaludin, Rosmawati and Adamu, Aliyu (2020) Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring. Malaysian Journal of Fundamental and Applied Sciences, 16 (4). pp. 422-428. ISSN 2289-599X http://dx.doi.org/10.11113/mjfas.v16n4.1682 DOI:10.11113/mjfas.v16n4.1682
institution Universiti Teknologi Malaysia
building UTM Library
collection Institutional Repository
continent Asia
country Malaysia
content_provider Universiti Teknologi Malaysia
content_source UTM Institutional Repository
url_provider http://eprints.utm.my/
language English
topic QD Chemistry
spellingShingle QD Chemistry
Abdul Razak, Fazira Ilyana
Abdul Wahab, Roswanira
Jamaludin, Rosmawati
Adamu, Aliyu
Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring
description Hartree Fock (HF) and density functional theory (DFT) methods based on a 3-21G set level were used to computationally assess the nonlinear optic (NLO) response of six ruthenium (Ru) arylalkynyl complexes. The low basis set of 3-21G was proved to provide adequate results with difference of only about 3% between calculation and experimental data. Substitution of Ru-phenyl with six simplified models of Ru-H and Ru-methyl complexes revealed that DFT-based calculations were more accurate than HF in estimating the NLO response. The calculated bond lengths and angles of Ru-methyl were in good agreement with Ru-phenyl. Given that the calculated C≡C stretching vibration and UV-vis maximum absorption for Ru-methyl was comparable to Ru-phenyl, with values corresponding to 2154.56 cm-1 and 460.93 nm, respectively. It was evident that Ru-H, Ru-methyl and Ru-phenyl complexes undergo intraligands π-π* and Laporte forbidden metal d-d transition. Henceforth, it is affirmed that calculations using simplified Ru-H complexes were as much as reliable as the full structure of Ru to assess the NLO response. Assessment of electron inductive effect on Ru-carbonyl (Ru-Co), Ru-cyclopentadienyl (Ru-Cp) and Ru- bipyridine (Ru-bpy) complexes revealed two absorption maxima that appeared in regions 320−375 nm and 382−460 nm, which represent an intraligand π-π* orbital and Laporte forbidden d-d-transition, respectively. Migration of electrons from Ru center to the bipyridine ligand suggests a greater electron acceptor effect than Ru center to the arylalkynyl group. However, Ru conjugated to an electron withdrawing group i.e. carbonyl tend to render lower NLO response while elevating HOMO - LUMO energy gap and Ru to Cα bond lengths.
format Article
author Abdul Razak, Fazira Ilyana
Abdul Wahab, Roswanira
Jamaludin, Rosmawati
Adamu, Aliyu
author_facet Abdul Razak, Fazira Ilyana
Abdul Wahab, Roswanira
Jamaludin, Rosmawati
Adamu, Aliyu
author_sort Abdul Razak, Fazira Ilyana
title Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring
title_short Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring
title_full Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring
title_fullStr Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring
title_full_unstemmed Tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring
title_sort tuning of nonlinear optic response properties for ruthenium alkynyl complexes via computational-guided structural tailoring
publisher Penerbit UTM Press
publishDate 2020
url http://eprints.utm.my/id/eprint/90955/1/FaziraIlyanaAbdul2020_TuningofNonlinearOpticResponseProperties.pdf
http://eprints.utm.my/id/eprint/90955/
http://dx.doi.org/10.11113/mjfas.v16n4.1682
_version_ 1702169625237651456
score 13.250246

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