Synthesis, mesomorphism, photophysics and device performance of liquid-crystalline pincer complexes of gold(<scp>iii</scp>)

Parker, Rachel R.; Liu, Denghui; Yu, Xiankang; Whitwood, Adrian C.; Zhu, Weiguo; Williams, J. A. Gareth; Wang, Yafei; Lynam, Jason M.; Bruce, Duncan W.

doi:10.1039/d0tc04839a

Cited by 14 publications

(37 citation statements)

References 67 publications

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“…It is instructive to consider the data in the light of both the other complexes described in this work and the all-hydrocarbon analogues published previously. 35 …”

Section: Liquid-crystalline Propertiesmentioning

confidence: 99%

“…Thus, while 16a–c all form Col h phases, the phase ranges are narrow once melted from the solid, and in one sense, it is perhaps remarkable that they are liquid crystals at all given that they possess three terminal chains. Indeed, of the all-hydrocarbon equivalents, 35 only one shows a mesophase and that is monotropic. Considering the data obtained from SAXS, the columnar lattice parameters for 16a and 16c are a = 33.1 and 35.9 Å, respectively, which are greater than the longest possible dimension of a complex ( ca 28 Å from the 4-hydrogen on the pyridyl ring to the terminal methyl group of the dodecyl chain on the pincer).…”

Section: Interpretation Of the Liquid Crystal Behaviormentioning

confidence: 99%

“…The UV–visible absorption spectra of complexes 16 – 21 , recorded in dichloromethane solution at room temperature, are essentially identical to the spectra of the corresponding complexes featuring hydrocarbon chains. 35 Since the fluorinated regions of the chains are electronically isolated from the core of the molecules through the −(CH 2 ) 2 – linkage, their inclusion would not be expected to alter the electronic energies of any of the orbitals involved in absorption transitions in this region of the spectrum, nor the oscillator strengths of the transitions.…”

Section: Photophysical Propertiesmentioning

confidence: 99%

“…The thermal behavior is summarized in Table and is represented graphically in Figure , while the X-ray data are collected in Table S1. It is instructive to consider the data in the light of both the other complexes described in this work and the all-hydrocarbon analogues published previously …”

Section: Liquid-crystalline Propertiesmentioning

confidence: 99%

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Synthesis, Mesomorphism, Photophysics, and Device Properties of Liquid-Crystalline Pincer Complexes of Gold(III) Containing Semiperfluorinated Chains

et al. 2022

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Gold(III) complexes of C ∧ N ∧ C -coordinating 2,6-diphenylpyridine pincer ligands with arylacetylide co-ligands are known triplet emitters at room temperature. We have reported previously that by functionalizing both the pincer ligand and the phenylacetylene with alkoxy chains, liquid crystallinity may be induced, with the complexes showing columnar mesophases. We now report new derivatives in which the phenylacetylene incorporates one, two, or three 1 H ,1 H ,2 H ,2 H -perfluoroalkyl chains. In terms of intermolecular interactions, solution 1 H NMR experiments suggest that the semiperfluoroalkyl chains promote a parallel, head-to-head arrangement of neighboring molecules relative to one another, rather than the anti-parallel, head-to-tail orientation found for the all-hydrocarbon materials. In terms of the liquid crystal properties, the complexes show columnar phases, with the addition of the more rigid fluorocarbon chains leading to a stabilization of both the crystal and liquid crystal mesophases. Mesophase temperature ranges were also wider. Interestingly, the amphiphilic nature of these complexes is evident through the observation of a frustrated columnar nematic phase between a Col r and a Col h phase, an observation recently reported in detail for one compound ( Liq. Cryst. , 2022, doi: 10.1080/02678292.2021.1991017 ). While calculation shows that, despite the “electronic insulation” provided by the dimethylene spacer group in the semiperfluoroalkyl chains, a small hypsochromic shift in one component of the absorption band is anticipated, experimentally this effect is not observed in the overall absorption envelope. Complexes with substituents in the 3,3′,4,4′-positions of the phenyl rings of the pincer ligand once more show higher-luminescence quantum yields than the analogues with substituents in the 4,4′-positions only, associated with the lower-energy-emissive state in the former. However, in contrast to the observations with all-hydrocarbon analogues, the luminescence quantum yield of the complexes with 3,3′,4,4′-substitution on the pincer increases as the number of semiperfluoroalkyl chains on the phenylacetylide increases, from 20% (one chain) to 34% (three chains). External quantum efficiencies in fabricated OLED devices are, however, low, attributed to the poor dispersion in the host materials on account of the fluorinated chains.

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“…It is instructive to consider the data in the light of both the other complexes described in this work and the all-hydrocarbon analogues published previously. 35 …”

Section: Liquid-crystalline Propertiesmentioning

confidence: 99%

Section: Interpretation Of the Liquid Crystal Behaviormentioning

confidence: 99%

Section: Photophysical Propertiesmentioning

confidence: 99%

Section: Liquid-crystalline Propertiesmentioning

confidence: 99%

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Synthesis, Mesomorphism, Photophysics, and Device Properties of Liquid-Crystalline Pincer Complexes of Gold(III) Containing Semiperfluorinated Chains

et al. 2022

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“…Since then, extensive research interest has been directed toward the design and synthesis of phosphorescent metal-based emitters for OLED applications. While precious metal complexes, such as those of iridium − and platinum, − are extensively used as the triplet emitters in phosphorescent OLEDs, advances in the field have led to the successful fabrication of efficient OLEDs based on complexes of osmium, − ruthenium, ,, gold, ,− and those based on earth-abundant elements, such as copper, , zinc, − tungsten, , and nickel . Apart from small molecules, the self-assembly of multiple metal centers into metal clusters and coordination polymers , has given rise to intriguing luminescence properties of metal-based materials.…”

Section: Introductionmentioning

confidence: 99%

Organic Light-Emitting Diodes Based on Luminescent Self-Assembled Materials of Copper(I)

2021

Energy Fuels

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Over the past decade, we have seen the rapid advancement in the technology of organic light-emitting diodes (OLEDs) toward practical applications. The high color contrast, wide viewing angles, good flexibility, and low power consumption of OLEDs have rendered them promising candidates for next-generation displays and solid-state lighting applications. Parallel to the optimization in device structures, of equal importance is the search for new classes of emitters. While conventional OLEDs mainly rely on triplet emitters based on precious metal complexes, such as those of platinum(II) and iridium(III), copper(I) self-assembled materials represent attractive alternatives with relatively low cost but comparable emission tunability. In this mini review, the recent progress in the development of copper(I) self-assembled materials, including copper(I) clusters and coordination polymers, as electroluminescent materials in OLEDs will be discussed.

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Solid‐State and Solution Self‐assembly Properties of Mono‐ and Bis‐acetylide Ru^II Complexes Bearing Hydrogen‐Bonding Amide Functions

et al. 2022

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In this work, we report our latest results regarding the selfassembly properties of two Ru-acetylides complexes and their corresponding free organic ligands, in solution and in the solid state. The four compounds show mesogenic properties, which we have rationalized thanks to extensive DSC, SAXS, POM, FTIR and molecular dynamic investigations. We clearly establish that hydrogen bonds stabilize the supramolecular structures, and that introducing the metal center and its coordination sphere induces large change in the liquid crystal properties. In addition, for the monoacetylide compound Ru 2 , solution-state studies helped us rationalize its supramolecular abilities. In particular, we demonstrate that Ru 2 follows an isodesmic growth supramolecular polymerization in aromatic solvent.

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Synthesis, mesomorphism, photophysics and device performance of liquid-crystalline pincer complexes of gold(iii)

Abstract: Emissive gold(iii) complexes with liquid-crystalline properties have been prepared, with most complexes showing a columnar hexagonal phase. The emissive response has been characterised in solution and in OLED devices.

Cited by 14 publications

References 67 publications

Synthesis, Mesomorphism, Photophysics, and Device Properties of Liquid-Crystalline Pincer Complexes of Gold(III) Containing Semiperfluorinated Chains

Synthesis, Mesomorphism, Photophysics, and Device Properties of Liquid-Crystalline Pincer Complexes of Gold(III) Containing Semiperfluorinated Chains

Organic Light-Emitting Diodes Based on Luminescent Self-Assembled Materials of Copper(I)

Solid‐State and Solution Self‐assembly Properties of Mono‐ and Bis‐acetylide Ru^II Complexes Bearing Hydrogen‐Bonding Amide Functions

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Synthesis, mesomorphism, photophysics and device performance of liquid-crystalline pincer complexes of gold(iii)

Abstract: Emissive gold(iii) complexes with liquid-crystalline properties have been prepared, with most complexes showing a columnar hexagonal phase. The emissive response has been characterised in solution and in OLED devices.

Cited by 14 publications

References 67 publications

Synthesis, Mesomorphism, Photophysics, and Device Properties of Liquid-Crystalline Pincer Complexes of Gold(III) Containing Semiperfluorinated Chains

Synthesis, Mesomorphism, Photophysics, and Device Properties of Liquid-Crystalline Pincer Complexes of Gold(III) Containing Semiperfluorinated Chains

Organic Light-Emitting Diodes Based on Luminescent Self-Assembled Materials of Copper(I)

Solid‐State and Solution Self‐assembly Properties of Mono‐ and Bis‐acetylide RuII Complexes Bearing Hydrogen‐Bonding Amide Functions

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Product

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Solid‐State and Solution Self‐assembly Properties of Mono‐ and Bis‐acetylide Ru^II Complexes Bearing Hydrogen‐Bonding Amide Functions