Effect of the donor–acceptor properties of ligands on the spectroscopic and electrochemical properties of mixed-ligand complexes of Pt(II) and Ir(III) with cyclometalated 2-phenylbenzothiazole

E. A. Katlenok, S. N. Smirnov, A. Yu Ivanov, S. V. Makarenko, K. P. Balashev

Research outputpeer-review

1 Citation (Scopus)

Abstract

The results of the spectroscopic NMR (1H, 13C, and 195Pt), infrared, optical, and voltammetric characteristics of the mixed-ligand complexes of Pt(II) and Ir(III) with metalated 2-phenylbenzothiazole and tert-butylisocyanide (tBuNC), acetonitrile (AN), ethylenediamine (En), O-ethyldithiocarbamate (Exn), and diethyldithiocarbamate (Dtc–) ions are presented. It is demonstrated that the change in donor–acceptor interaction of ligands tBuNC, AN, En, Exn, and Dtc with metal leads to an increase in the energy of the highest occupied molecular orbital of the complexes and is accompanied by a shift of the cathode potential of the metal-centered oxidation, a bathochromic shift of the spin-allowed and spin-forbidden metal-tocyclometalated ligand optical charge transfer transitions, and an increase the degree of mixing of the 1MLCT and triplet intraligand states, responsible for the phosphorescence of the complexes.

Original languageEnglish
Pages (from-to)426-434
Number of pages9
JournalOptics and Spectroscopy (English translation of Optika i Spektroskopiya)
Volume122
Issue number3
DOIs
Publication statusPublished - 1 Mar 2017

Fingerprint

ethylenediamine
Electrochemical properties
Ditiocarb
Metals
Ligands
Acetonitrile
ligands
acetonitrile
Phosphorescence
shift
Molecular orbitals
phosphorescence
metals
atomic energy levels
Charge transfer
molecular orbitals
Cathodes
cathodes
charge transfer
Nuclear magnetic resonance

Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Atomic and Molecular Physics, and Optics

Cite this

@article{1a4db3e8d00b46078ec99222b5d27632,
title = "Effect of the donor–acceptor properties of ligands on the spectroscopic and electrochemical properties of mixed-ligand complexes of Pt(II) and Ir(III) with cyclometalated 2-phenylbenzothiazole",
abstract = "The results of the spectroscopic NMR (1H, 13C, and 195Pt), infrared, optical, and voltammetric characteristics of the mixed-ligand complexes of Pt(II) and Ir(III) with metalated 2-phenylbenzothiazole and tert-butylisocyanide (tBuNC), acetonitrile (AN), ethylenediamine (En), O-ethyldithiocarbamate (Exn–), and diethyldithiocarbamate (Dtc–) ions are presented. It is demonstrated that the change in donor–acceptor interaction of ligands tBuNC, AN, En, Exn–, and Dtc– with metal leads to an increase in the energy of the highest occupied molecular orbital of the complexes and is accompanied by a shift of the cathode potential of the metal-centered oxidation, a bathochromic shift of the spin-allowed and spin-forbidden metal-tocyclometalated ligand optical charge transfer transitions, and an increase the degree of mixing of the 1MLCT and triplet intraligand states, responsible for the phosphorescence of the complexes.",
author = "Katlenok, {E. A.} and Smirnov, {S. N.} and Ivanov, {A. Yu} and Makarenko, {S. V.} and Balashev, {K. P.}",
year = "2017",
month = "3",
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language = "English",
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pages = "426--434",
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TY - JOUR

T1 - Effect of the donor–acceptor properties of ligands on the spectroscopic and electrochemical properties of mixed-ligand complexes of Pt(II) and Ir(III) with cyclometalated 2-phenylbenzothiazole

AU - Katlenok, E. A.

AU - Smirnov, S. N.

AU - Ivanov, A. Yu

AU - Makarenko, S. V.

AU - Balashev, K. P.

PY - 2017/3/1

Y1 - 2017/3/1

N2 - The results of the spectroscopic NMR (1H, 13C, and 195Pt), infrared, optical, and voltammetric characteristics of the mixed-ligand complexes of Pt(II) and Ir(III) with metalated 2-phenylbenzothiazole and tert-butylisocyanide (tBuNC), acetonitrile (AN), ethylenediamine (En), O-ethyldithiocarbamate (Exn–), and diethyldithiocarbamate (Dtc–) ions are presented. It is demonstrated that the change in donor–acceptor interaction of ligands tBuNC, AN, En, Exn–, and Dtc– with metal leads to an increase in the energy of the highest occupied molecular orbital of the complexes and is accompanied by a shift of the cathode potential of the metal-centered oxidation, a bathochromic shift of the spin-allowed and spin-forbidden metal-tocyclometalated ligand optical charge transfer transitions, and an increase the degree of mixing of the 1MLCT and triplet intraligand states, responsible for the phosphorescence of the complexes.

AB - The results of the spectroscopic NMR (1H, 13C, and 195Pt), infrared, optical, and voltammetric characteristics of the mixed-ligand complexes of Pt(II) and Ir(III) with metalated 2-phenylbenzothiazole and tert-butylisocyanide (tBuNC), acetonitrile (AN), ethylenediamine (En), O-ethyldithiocarbamate (Exn–), and diethyldithiocarbamate (Dtc–) ions are presented. It is demonstrated that the change in donor–acceptor interaction of ligands tBuNC, AN, En, Exn–, and Dtc– with metal leads to an increase in the energy of the highest occupied molecular orbital of the complexes and is accompanied by a shift of the cathode potential of the metal-centered oxidation, a bathochromic shift of the spin-allowed and spin-forbidden metal-tocyclometalated ligand optical charge transfer transitions, and an increase the degree of mixing of the 1MLCT and triplet intraligand states, responsible for the phosphorescence of the complexes.

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U2 - 10.1134/S0030400X17030110

DO - 10.1134/S0030400X17030110

M3 - Article

VL - 122

SP - 426

EP - 434

JO - OPTICS AND SPECTROSCOPY

JF - OPTICS AND SPECTROSCOPY

SN - 0030-400X

IS - 3

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