Electrochemiluminescent Systems as Devices and Sensors

Kapturkiewicz, Andrzej

doi:10.1002/9780470583463.ch16

Cited by 17 publications

(21 citation statements)

References 310 publications

(390 reference statements)

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“…Others from the investigated Ir(pqcm) 2 (N^N) + chelates, with more extended π-aromatic N^N co-ligands, were distinctly less efficient, most probably due to smaller values of their emission quantum efficiencies as could be concluded taking into account the same sequence of the ECL intensities and the quantum efficiencies of the excited 3* Ir(pqcm) 2 (N^N) + states. Low ECL efficiency reported by Qin [ 97 ] for the ionic Ir(ppy) 2 (N^N) + chelate with 4′,5′-dimethyldithiotetrathiafulvenyl[4,5-f][ 1 , 10 ]phenanthroline co-ligand remains in agreement with the results presented by other authors. The ECL peak intensity of the studied complex was half that of Ir(ppy) 2 (phen) + in the ECL processes investigated in CH 2 Cl 2 solution containing ( n -C 4 H 9 ) 4 NClO 4 as the supporting electrolyte and TPrA as the ECL co-reactant.…”

Section: Ecl Properties Of the Heteroleptic Iridium(iii) Chelatessupporting

confidence: 89%

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Cyclometalated iridium(III) chelates—a new exceptional class of the electrochemiluminescent luminophores

Kapturkiewicz

2016

Anal Bioanal Chem

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Recent development of the phosphorescent cyclometalated iridium(III) chelates has enabled, due to their advantageous electrochemical and photo-physical properties, important breakthroughs in many photonic applications. This particular class of 5d6 ion complexes has attracted increasing interest because of their potential application in electroluminescence devices with a nearly 100 % internal quantum efficiency for the conversion of electric energy to photons. Similar to electroluminescence, the cyclometalated iridium(III) chelates have been successfully applied in the electricity-to-light conversion by means of the electrochemiluminescence (ECL) processes. The already reported ECL systems utilizing the title compounds exhibit extremely large ECL efficiencies that allow one to envisage many potential application for them, especially in further development of ECL-based analytical techniques. This review, based on recently published papers, focuses on the ECL properties of this very exciting class of organometallic luminophores. The reported work, describing results from fundamental as well as application-oriented investigations, will be surveyed and briefly discussed.Graphical abstractDepending on the chemical nature of the cyclometalated irdium(III) chelate different colours of the emitted light can be produced during electrochemical excitation.

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Section: Ecl Properties Of the Heteroleptic Iridium(iii) Chelatessupporting

confidence: 89%

“…A third reduction wave, corresponding to Ir(ppy) 3 3− formation could not be observed under the experimental conditions because of the redox potential value being more negative than the solvent cathodic limit. Adapted from ref [ 10 ] …”

Section: Ecl Properties Of the Homoleptic Iridium(iii) Chelatesmentioning

confidence: 99%

Cyclometalated iridium(III) chelates—a new exceptional class of the electrochemiluminescent luminophores

Kapturkiewicz

2016

Anal Bioanal Chem

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“…Table 1 , and the competition between localization and delocalizsation in their excited states 2 . Beyond their intrinsic scientific interest, understanding and controlling this phenomenology is further motivated by the potential for the use of such complexes in diverse applications including dye-sensitized solar cells, non-linear optics, photocatalysis, biological imaging, chemical and biological sensing, photodynamic therapy, light-emitting electro-chemical cells and organic light emitting diodes 1 3 4 5 6 . As many of these applications make use of the excited state properties of these complexes a deep understanding of the low-energy excited states, particularly the lowest energy triplet state, T 1 , is required to enable the rational design of new complexes.…”

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confidence: 99%

Conservation laws, radiative decay rates and excited state localization in organometallic complexes with strong spin-orbit coupling

Powell

2015

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There is longstanding fundamental interest in 6-fold coordinated d6 () transition metal complexes such as [Ru(bpy)3]2+ and Ir(ppy)3, particularly their phosphorescence. This interest has increased with the growing realisation that many of these complexes have potential uses in applications including photovoltaics, imaging, sensing, and light-emitting diodes. In order to design new complexes with properties tailored for specific applications a detailed understanding of the low-energy excited states, particularly the lowest energy triplet state, T1, is required. Here we describe a model of pseudo-octahedral complexes based on a pseudo-angular momentum representation and show that the predictions of this model are in excellent agreement with experiment - even when the deviations from octahedral symmetry are large. This model gives a natural explanation of zero-field splitting of T1 and of the relative radiative rates of the three sublevels in terms of the conservation of time-reversal parity and total angular momentum modulo two. We show that the broad parameter regime consistent with the experimental data implies significant localization of the excited state.

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“…Simplified Jablonski energy diagram depicting the ground state (GS) and the triplet emissive excited states involved in the photophysics of these complexes; including e.g., the excited state involved in emission, T em ; the metal-centered triplet excited state, 3 MC; and a higher-lying triplet excited state, T m .…”

Section: Figurementioning

confidence: 99%

“…For the latter complexes, their S 0 and T 1 optimized geometries are rather similar; being the main geometrical rearrangements when moving from S 0 to T 1 the change in some of the Ptligand bond distances (see Figure 4). The spin density plot of their T 1 states highlights the predominant metal-to-ligand charge transfer ( 3 MLCT) character for the complexes (e.g., 5) with the exception of that of complex 1, which can be better described as a mixed 3 MC/ 3 MLCT/ 3 LC state. For Case II complexes a UB3LYP optimization of the lowest triplet excited state leads to a metal-centered state (i.e., 3 MC), as clearly highlighted by inspecting their spin density distribution plot (see e.g., for complex 7 in Figure 4).…”

Section: Phosphorescent Energy Calculations In Complexes 1-12mentioning

confidence: 99%

A Computational Protocol to Calculate the Phosphorescence Energy of Pt (II) Complexes: Is the lowest triplet excited state always involved in emission? A Comprehensive Benchmark Study

Kumar

Escudero

2021

Preprint

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The reliable calculation of the phosphorescence energies of phosphor materials is at the core of designing efficient phosphorescent organic light-emitting diodes (PhOLEDs). Therefore, it is of paramount importance to have a robust computational protocol to perform those calculations in a black-box manner. In this work, we use Domain Based Local Pair Natural Orbital Coupled Cluster theory with single, double and perturbative triple excitation (DLPNO-CCSD(T)) calculations to attain the phosphorescence energies of a large pool of Pt (II) complexes. Several approaches to incorporate relativistic effects in our calculations were tested. In addition, we have used the DLPNO-CCSD(T) values (i.e., our best theoretical values) to assess the performance of different flavors of density functional theory including pure, hybrid, meta-hybrid, and range-separated functionals. Among the tested functionals, the M06HF functional provides the best values as compared with the DLPNO-CCSD(T) ones, with a mean absolute deviation (MAD) value of 0.14 eV. In its turn, and thanks to the increased accuracy achieved in the calculation of phosphorescence energies, we also demonstrate that not all the investigated complexes emit from their lowest lying triplet-state (T 1 ). The outlier complexes include different complex photophysical scenarios and both Kasha and anti-Kasha types of complexes. Finally, we provide a general computational protocol to pre-screen whether T 1 is actually the emissive state and to accurately calculate the phosphorescence energies of Pt (II) complexes.

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Electrochemiluminescent Systems as Devices and Sensors

Cited by 17 publications

References 310 publications

Cyclometalated iridium(III) chelates—a new exceptional class of the electrochemiluminescent luminophores

Cyclometalated iridium(III) chelates—a new exceptional class of the electrochemiluminescent luminophores

Conservation laws, radiative decay rates and excited state localization in organometallic complexes with strong spin-orbit coupling

A Computational Protocol to Calculate the Phosphorescence Energy of Pt (II) Complexes: Is the lowest triplet excited state always involved in emission? A Comprehensive Benchmark Study

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