Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes

Kamelah S. Al-Rashdi; Bandar A. Babgi; Cigdem Sahin; Naser E. Eltayeb; Graeme J. Moxey; Mark G. Humphrey; Amal S. Basaleh

doi:10.1016/j.molstruc.2018.01.026

Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes

Kamelah S. Al-Rashdi, Bandar A. Babgi^*, Cigdem Sahin, Naser E. Eltayeb, Graeme J. Moxey, Mark G. Humphrey, Amal S. Basaleh

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

The complex with the formula [Ru(bpy)₂(2,3-diaminonaphthalene)][PF₆] (5) was synthesized and characterized by ¹H NMR spectroscopy, mass spectrometry and elemental analysis. A set of previously reported complexes with the formula [Ru(bpy)₂(diamine)][PF₆]{diamine = 1,2-diaminoethane (2), o-phenylenediamine (3), 1,2-diaminocyclohexane (4) } was synthesized and crystal structures were obtained for complexes 3 and 4. UV–vis absorption spectra of the complexes 2–5 were collected and compared to that of [Ru(bpy)₃][PF₆]₂ (1), showing that the MLCT band is red-shifted upon introducing the diamine ligands in place of bipyridine. Emission spectra, excited-state lifetimes and emission quantum yields were collected at room temperature for the complexes 1–5, showing considerable changes in the photophysical characteristics upon the introductions of the diamine. The emission spectrum of 5 exhibits an intense emission in the far red-NIR region when excited at 510 nm. The cyclic voltammograms of the complexes 1–5 show one oxidation peak between 0.98 V and 1.15 V which is attributed to the Ru(II)/Ru(III) oxidation couple. Calculated HOMO and LUMO energy levels from both electrochemical data and theoretical calculations suggest a lower HOMO energy level for complex 1 than the diamino-containing complexes, presumably due to the stronger ligand field of the bipyridine.

Original language	English
Pages (from-to)	197-204
Number of pages	8
Journal	Journal of Molecular Structure
Volume	1158
DOIs	https://doi.org/10.1016/j.molstruc.2018.01.026
Publication status	Published - 15 Apr 2018

Access to Document

10.1016/j.molstruc.2018.01.026

Cite this

@article{0fc82b403c8a4dd499a3c82342caf6a3,

title = "Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes",

abstract = "The complex with the formula [Ru(bpy)2(2,3-diaminonaphthalene)][PF6] (5) was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry and elemental analysis. A set of previously reported complexes with the formula [Ru(bpy)2(diamine)][PF6]{diamine = 1,2-diaminoethane (2), o-phenylenediamine (3), 1,2-diaminocyclohexane (4) } was synthesized and crystal structures were obtained for complexes 3 and 4. UV–vis absorption spectra of the complexes 2–5 were collected and compared to that of [Ru(bpy)3][PF6]2 (1), showing that the MLCT band is red-shifted upon introducing the diamine ligands in place of bipyridine. Emission spectra, excited-state lifetimes and emission quantum yields were collected at room temperature for the complexes 1–5, showing considerable changes in the photophysical characteristics upon the introductions of the diamine. The emission spectrum of 5 exhibits an intense emission in the far red-NIR region when excited at 510 nm. The cyclic voltammograms of the complexes 1–5 show one oxidation peak between 0.98 V and 1.15 V which is attributed to the Ru(II)/Ru(III) oxidation couple. Calculated HOMO and LUMO energy levels from both electrochemical data and theoretical calculations suggest a lower HOMO energy level for complex 1 than the diamino-containing complexes, presumably due to the stronger ligand field of the bipyridine.",

keywords = "Electrochemical properties, Luminescence, Photophysical properties, Polypyridyls, Ruthenium(II)",

author = "Al-Rashdi, {Kamelah S.} and Babgi, {Bandar A.} and Cigdem Sahin and Eltayeb, {Naser E.} and Moxey, {Graeme J.} and Humphrey, {Mark G.} and Basaleh, {Amal S.}",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier B.V.",

year = "2018",

month = apr,

day = "15",

doi = "10.1016/j.molstruc.2018.01.026",

language = "English",

volume = "1158",

pages = "197--204",

journal = "Journal of Molecular Structure",

issn = "0022-2860",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes

AU - Al-Rashdi, Kamelah S.

AU - Babgi, Bandar A.

AU - Sahin, Cigdem

AU - Eltayeb, Naser E.

AU - Moxey, Graeme J.

AU - Humphrey, Mark G.

AU - Basaleh, Amal S.

PY - 2018/4/15

Y1 - 2018/4/15

N2 - The complex with the formula [Ru(bpy)2(2,3-diaminonaphthalene)][PF6] (5) was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry and elemental analysis. A set of previously reported complexes with the formula [Ru(bpy)2(diamine)][PF6]{diamine = 1,2-diaminoethane (2), o-phenylenediamine (3), 1,2-diaminocyclohexane (4) } was synthesized and crystal structures were obtained for complexes 3 and 4. UV–vis absorption spectra of the complexes 2–5 were collected and compared to that of [Ru(bpy)3][PF6]2 (1), showing that the MLCT band is red-shifted upon introducing the diamine ligands in place of bipyridine. Emission spectra, excited-state lifetimes and emission quantum yields were collected at room temperature for the complexes 1–5, showing considerable changes in the photophysical characteristics upon the introductions of the diamine. The emission spectrum of 5 exhibits an intense emission in the far red-NIR region when excited at 510 nm. The cyclic voltammograms of the complexes 1–5 show one oxidation peak between 0.98 V and 1.15 V which is attributed to the Ru(II)/Ru(III) oxidation couple. Calculated HOMO and LUMO energy levels from both electrochemical data and theoretical calculations suggest a lower HOMO energy level for complex 1 than the diamino-containing complexes, presumably due to the stronger ligand field of the bipyridine.

AB - The complex with the formula [Ru(bpy)2(2,3-diaminonaphthalene)][PF6] (5) was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry and elemental analysis. A set of previously reported complexes with the formula [Ru(bpy)2(diamine)][PF6]{diamine = 1,2-diaminoethane (2), o-phenylenediamine (3), 1,2-diaminocyclohexane (4) } was synthesized and crystal structures were obtained for complexes 3 and 4. UV–vis absorption spectra of the complexes 2–5 were collected and compared to that of [Ru(bpy)3][PF6]2 (1), showing that the MLCT band is red-shifted upon introducing the diamine ligands in place of bipyridine. Emission spectra, excited-state lifetimes and emission quantum yields were collected at room temperature for the complexes 1–5, showing considerable changes in the photophysical characteristics upon the introductions of the diamine. The emission spectrum of 5 exhibits an intense emission in the far red-NIR region when excited at 510 nm. The cyclic voltammograms of the complexes 1–5 show one oxidation peak between 0.98 V and 1.15 V which is attributed to the Ru(II)/Ru(III) oxidation couple. Calculated HOMO and LUMO energy levels from both electrochemical data and theoretical calculations suggest a lower HOMO energy level for complex 1 than the diamino-containing complexes, presumably due to the stronger ligand field of the bipyridine.

KW - Electrochemical properties

KW - Luminescence

KW - Photophysical properties

KW - Polypyridyls

KW - Ruthenium(II)

UR - http://www.scopus.com/inward/record.url?scp=85040672820&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2018.01.026

DO - 10.1016/j.molstruc.2018.01.026

M3 - Article

SN - 0022-2860

VL - 1158

SP - 197

EP - 204

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

ER -

Diamines as auxiliary ligands for tuning photophysical and electrochemical properties of Ruthenium(II) polypyridyl complexes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this