Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^N^C Pincer Ligand and Bipyridine/Terpyridine

Kai-Wa Io; Sze-Wing Ng; Chi-Fung Yeung; Chun-Yuen Wong

doi:10.1002/ejic.202000411

Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^{^}N^{^}C Pincer Ligand and Bipyridine/Terpyridine

Kai-Wa Io, Sze-Wing Ng, Chi-Fung Yeung, Chun-Yuen Wong^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

4 Citations (Scopus)

Abstract

Rhodium(III) complexes containing tridentate N-heterocyclic carbene (NHC)-based pincer ligand in the form of [Rh(C^{^}N^{^}C)(N^{^}N)X]²⁺ and [Rh(C^{^}N^{^}C)(tpy)]³⁺ (C^{^}N^{^}C = (2,6-bis(1-butylimidazol-2-ylidene)pyridine (C¹^{^}N^{^}C¹) or 2,6-bis(3-butylbenzimidazol-2-ylidene)pyridine (C²^{^}N^{^}C²); N^{^}N = bipyridine-type aromatic diimines; tpy = 2,2':6',2''-terpyridine; X = Cl or Br) were prepared. Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations revealed the lowest-energy electronic transition associated with these complexes are different from their Ru(II), Os(II) and Ir(III) analogues. The Rh(III) complexes exhibit luminescent behavior at 77 K upon photoexcitation. The impact of the C^{^}N^{^}C pincer ligands on the photophysics of the Rh(III) complexes was investigated.

Original language	English
Pages (from-to)	2343-2351
Number of pages	9
Journal	European Journal of Inorganic Chemistry
Volume	2020
Issue number	24
Online published	15 May 2020
DOIs	https://doi.org/10.1002/ejic.202000411
Publication status	Published - 30 Jun 2020

Funding

The work described in this paper was supported by the Research Grants Council of Hong Kong SAR (CityU 11207117) and City University of Hong Kong (7005096,7005257,9680206). We are grateful to Dr. Shek-Man Yiu for X-ray diffraction data collection.

Research Keywords

DFT calculations
Photophysics
Pincer ligand
Rhodium

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@article{15224cca417e46f699fce2bb925a2f69,

title = "Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^N^C Pincer Ligand and Bipyridine/Terpyridine",

abstract = "Rhodium(III) complexes containing tridentate N-heterocyclic carbene (NHC)-based pincer ligand in the form of [Rh(C^N^C)(N^N)X]2+ and [Rh(C^N^C)(tpy)]3+ (C^N^C = (2,6-bis(1-butylimidazol-2-ylidene)pyridine (C1^N^C1) or 2,6-bis(3-butylbenzimidazol-2-ylidene)pyridine (C2^N^C2); N^N = bipyridine-type aromatic diimines; tpy = 2,2':6',2''-terpyridine; X = Cl or Br) were prepared. Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations revealed the lowest-energy electronic transition associated with these complexes are different from their Ru(II), Os(II) and Ir(III) analogues. The Rh(III) complexes exhibit luminescent behavior at 77 K upon photoexcitation. The impact of the C^N^C pincer ligands on the photophysics of the Rh(III) complexes was investigated.",

keywords = "DFT calculations, Photophysics, Pincer ligand, Rhodium, DFT calculations, Photophysics, Pincer ligand, Rhodium, DFT calculations, Photophysics, Pincer ligand, Rhodium",

author = "Kai-Wa Io and Sze-Wing Ng and Chi-Fung Yeung and Chun-Yuen Wong",

year = "2020",

month = jun,

day = "30",

doi = "10.1002/ejic.202000411",

language = "English",

volume = "2020",

pages = "2343--2351",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag GmbH",

number = "24",

}

Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^{^}N^{^}C Pincer Ligand and Bipyridine/Terpyridine. / Io, Kai-Wa ; Ng, Sze-Wing ; Yeung, Chi-Fung et al.
In: European Journal of Inorganic Chemistry, Vol. 2020, No. 24, 30.06.2020, p. 2343-2351.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^N^C Pincer Ligand and Bipyridine/Terpyridine

AU - Io, Kai-Wa

AU - Ng, Sze-Wing

AU - Yeung, Chi-Fung

AU - Wong, Chun-Yuen

PY - 2020/6/30

Y1 - 2020/6/30

N2 - Rhodium(III) complexes containing tridentate N-heterocyclic carbene (NHC)-based pincer ligand in the form of [Rh(C^N^C)(N^N)X]2+ and [Rh(C^N^C)(tpy)]3+ (C^N^C = (2,6-bis(1-butylimidazol-2-ylidene)pyridine (C1^N^C1) or 2,6-bis(3-butylbenzimidazol-2-ylidene)pyridine (C2^N^C2); N^N = bipyridine-type aromatic diimines; tpy = 2,2':6',2''-terpyridine; X = Cl or Br) were prepared. Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations revealed the lowest-energy electronic transition associated with these complexes are different from their Ru(II), Os(II) and Ir(III) analogues. The Rh(III) complexes exhibit luminescent behavior at 77 K upon photoexcitation. The impact of the C^N^C pincer ligands on the photophysics of the Rh(III) complexes was investigated.

AB - Rhodium(III) complexes containing tridentate N-heterocyclic carbene (NHC)-based pincer ligand in the form of [Rh(C^N^C)(N^N)X]2+ and [Rh(C^N^C)(tpy)]3+ (C^N^C = (2,6-bis(1-butylimidazol-2-ylidene)pyridine (C1^N^C1) or 2,6-bis(3-butylbenzimidazol-2-ylidene)pyridine (C2^N^C2); N^N = bipyridine-type aromatic diimines; tpy = 2,2':6',2''-terpyridine; X = Cl or Br) were prepared. Spectroscopic comparisons and time-dependent density functional theory (TD-DFT) calculations revealed the lowest-energy electronic transition associated with these complexes are different from their Ru(II), Os(II) and Ir(III) analogues. The Rh(III) complexes exhibit luminescent behavior at 77 K upon photoexcitation. The impact of the C^N^C pincer ligands on the photophysics of the Rh(III) complexes was investigated.

KW - DFT calculations

KW - Photophysics

KW - Pincer ligand

KW - Rhodium

KW - DFT calculations

KW - Photophysics

KW - Pincer ligand

KW - Rhodium

KW - DFT calculations

KW - Photophysics

KW - Pincer ligand

KW - Rhodium

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U2 - 10.1002/ejic.202000411

DO - 10.1002/ejic.202000411

M3 - RGC 21 - Publication in refereed journal

AN - SCOPUS:85086997989

SN - 1434-1948

VL - 2020

SP - 2343

EP - 2351

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 24

ER -

Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^{^}N^{^}C Pincer Ligand and Bipyridine/Terpyridine

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GRF: Rational Design of Photoresponsive Anti-Cancer Drug Delivery Nanoparticles

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Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^N^C Pincer Ligand and Bipyridine/Terpyridine

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Funding

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GRF: Rational Design of Photoresponsive Anti-Cancer Drug Delivery Nanoparticles

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Synthesis, Spectroscopic and Computational Studies of Rhodium(III) Complexes Bearing N-Heterocyclic Carbene-Based C^{^}N^{^}C Pincer Ligand and Bipyridine/Terpyridine