The Luminescence Rigidochromic Effect Exhibited by Organometallic Complexes: Rationale and Applications

Lees, Alistair J.

doi:10.1080/02603599508032711

Cited by 140 publications

(118 citation statements)

References 38 publications

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“…The cycloplatinated complexes 1 and 2 also show a small blue shift of ca. 5 nm on cooling to 77 K. This observation could be attributed to the increased rigidity in the frozen state, which has usually been described as rigidochromism (seeFigure 3andTable 2) 27,[52][53][54][55][56]. Due to combination of strong-fields of aryl and C ˄ N cyclometalating ligands, the complexes…”

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confidence: 85%

Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

et al. 2015

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To investigate the factors influencing the luminescent properties of cycloplatinated complexes containing aryl and SMe 2 ligands, a detailed study of the photophysical and structural properties of the complexes [Pt(p-MeC 6 H 4 )(C^N)(SMe 2 )], (C^N= benzo[h]quinolate (bzq), 1, or 2-phenylpyridinate (ppy), 2), was conducted in solution and solid state at different temperatures. Density functional theory (DFT) and Time-dependent density functional theory (TD-DFT) investigations were carried out on both the singlet (S 0 , ground) and triplet (T 1 , excited) states of these complexes for explanation of the electronic structures, absorption and emission spectra. In the solid state, these complexes display an intense phosphorescence emission which was red-shifted from 2 to 1 due to expanding of π conjugated system in cyclometalated bzq ligand. These complexes are strongly emissive in 77 K, giving emission peaks similar to those observed at ambient temperature. The complex 1 in deoxygenated CH 2 Cl 2 solution (at low concentration) gave a phosphorescence band which 2 was accompanied by a higher-energy fluorescence band (ascribed to 1 LC transition, centered on bzq ligand), and these bands were disappeared when a concentrated solution or glassy state (77 K) of the complex is in use. On the basis of theoretical calculations, the HOMO level is a mixture of platinum center and ligand orbitals, while the LUMO level is predominantly C^N ligand based. Lowest-lying excited state responsible for the phosphorescence emission (with a significantly long lifetime) is originated from mixed 3 ILCT/ 3 MLCT with some 3 L'LCT excited state and the emission is red shifted to corresponding free cyclometallating ligand.

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confidence: 85%

Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

et al. 2015

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“…The luminescent properties of L1 ‐ and L2 ‐bridged complexes measured in 2‐MeTHF at 77 K are collected in Table . All complexes were highly emissive at 77 K. In general, the emission maxima of these complexes showed hypsochromic shifts when compared to the spectra acquired at room temperature, which is commonly seen in the typical Re I diimine tricarbonyl complexes and this is referred to the rigidochromic effect . The excited state decay of L1 ‐bridged complexes shown in Table followed multi‐exponential kinetics.…”

Section: Resultsmentioning

confidence: 81%

“…The excited decay at 77 K for these complexes required bi‐exponential parameters to fit the process. Emissions coming from 3 LC states are relatively insensitive to surrounding medium and temperature due to the minimal redistribution of electron density with respect to the solvent dielectric field . This could be the consequence of hypsochromic shift of the 3 MLCT state to a higher energy than the 3 LC state.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Electrochemical and Photophysical Properties of 2,4,6‐Tripyridyl‐1,3,5‐Triazine‐Bridged Trinuclear Diimine Rhenium(I) Tricarbonyl Complexes

et al. 2017

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Two series of trinuclear diimine Re I tricarbonyl complexes bridged by 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (L1) or 2,4,6-tri(pyridin-3-yl)-1,3,5-triazine (L2) have been synthesized and characterized. These two series of trinuclear complexes show distinctly different photophysical and electrochemical properties. The L2-bridged complexes exhibit strong luminescence and relatively long emission lifetimes in room-temperature solution, which are typical of decay from 3 MLCT excited states, whereas L1-bridged complexes show only very weak lu-

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“…Interestingly, the emission maxima are significantly hypsochromically shifted of up to 72 nm for C7 compared to the maxima in solution. This shift can be explained by the luminescence rigodochromic effect as well as by the smaller changes of the molecular geometry in the solid state upon excitation . Linfoot et al.…”

Section: Resultsmentioning

confidence: 99%

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties

Giereth

Mengele

Frey

et al. 2020

Chemistry A European J

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A series of seven homoleptic CuI complexes based on hetero‐bidentate P^N ligands was synthesized and comprehensively characterized. In order to study structure–property relationships, the type, size, number and configuration of substituents at the phosphinooxazoline (phox) ligands were systematically varied. To this end, a combination of X‐ray diffraction, NMR spectroscopy, steady‐state absorption and emission spectroscopy, time‐resolved emission spectroscopy, quenching experiments and cyclic voltammetry was used to assess the photophysical and electrochemical properties. Furthermore, time‐dependent density functional theory calculations were applied to also analyze the excited state structures and characteristics. Surprisingly, a strong dependency on the chirality of the respective P^N ligand was found, whereas the specific kind and size of the different substituents has only a minor impact on the properties in solution. Most importantly, all complexes except C3 are photostable in solution and show fully reversible redox processes. Sacrificial reductants were applied to demonstrate a successful electron transfer upon light irradiation. These properties render this class of photosensitizers as potential candidates for solar energy conversion issues.

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The Luminescence Rigidochromic Effect Exhibited by Organometallic Complexes: Rationale and Applications

Cited by 140 publications

References 38 publications

Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

Synthesis, Electrochemical and Photophysical Properties of 2,4,6‐Tripyridyl‐1,3,5‐Triazine‐Bridged Trinuclear Diimine Rhenium(I) Tricarbonyl Complexes

Copper(I) Phosphinooxazoline Complexes: Impact of the Ligand Substitution and Steric Demand on the Electrochemical and Photophysical Properties

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