Excimer‐ und Exciplex‐Bildung in durch aurophile Wechselwirkungen präkonditionierten Gold(I)‐ Komplexen

Schmidbaur, Hubert; Raubenheimer, Helgard G.

doi:10.1002/ange.201916255

Angewandte Chemie

2020

DOI: 10.1002/ange.201916255

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Excimer‐ und Exciplex‐Bildung in durch aurophile Wechselwirkungen präkonditionierten Gold(I)‐ Komplexen

Hubert Schmidbaur

Helgard G. Raubenheimer²

Abstract: Excimere und Exciplexe sind definiert als Aggregate von Atomen oder Molekülen A/A′, in denen es nur in angeregten Zuständen [A2]* und [AA′]* zu interatomaren/‐molekularen Bindungen kommt. Ihre Bildung wurde weithin bekannt durch ihre Bedeutung in Gasphasen‐Lasertechnologien. Jüngste Untersuchungen in der Goldchemie haben der Excimer‐ und Exciplex‐Chemie ein neues Gebiet eröffnet, das hauptsächlich durch die Aggregation von Gold(I)‐Verbindungen (AuI(5d10)) über aurophile Kontakte bedingt wird. In den zugehörige… Show more

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Cited by 3 publications

References 243 publications

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Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

et al. 2022

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Gold complexes can generate excimers ([Au2]→[Au2]*) and exciplexes ([Au3]→[Au3]*) with light excitation. Four GdIII and YIII complexes were assembled with dimeric {[Au(SCN)2]−}2 and trimeric {[Au(SCN)2]−}3 bis(thiocyanato)gold(I) counterions. The vibrational signature associated with the Au⋅⋅⋅Au vibrational mode was probed with ultralow frequency (ULF) Raman spectroscopy as a function of temperature. Emission spectroscopy was used to explore photophysical properties. Two broad features in the high‐ and low‐energy regions were associated with the fluorescence and phosphorescence of the gold entities, respectively. Temperature‐dependent luminescence measurements showed that the emission color can be tuned from blue to green via cyan and white. Hence, these complexes can act as colorimetric thermometers. Additionally, a ratiometric thermal sensing ability was incorporated with high sensitivity up to 5 % K−1 in the cryogenic temperature range.

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Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

et al. 2022

View full text Add to dashboard Cite

show abstract

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

et al. 2022

View full text Add to dashboard Cite

Gold complexes can generate excimers ([Au 2 ]![Au 2 ]*) and exciplexes ([Au 3 ]![Au 3 ]*) with light excitation. Four Gd III and Y III complexes were assembled with dimeric {[Au(SCN) 2 ] À } 2 and trimeric {[Au(SCN) 2 ] À } 3 bis(thiocyanato)gold(I) counterions. The vibrational signature associated with the Au•••Au vibrational mode was probed with ultralow frequency (ULF) Raman spectroscopy as a function of temperature.Emission spectroscopy was used to explore photophysical properties. Two broad features in the high-and lowenergy regions were associated with the fluorescence and phosphorescence of the gold entities, respectively. Temperature-dependent luminescence measurements showed that the emission color can be tuned from blue to green via cyan and white. Hence, these complexes can act as colorimetric thermometers. Additionally, a ratiometric thermal sensing ability was incorporated with high sensitivity up to 5 % K À 1 in the cryogenic temperature range.

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Formation of Excimers in Isoquinolinyl Pyrazolate Pt(II) Complexes: Role of Cooperativity Effects

et al. 2020

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The interplay between noncovalent interactions involving metal complexes may lead to the formation of aggregates (i.e., ground state dimers, trimers, n-mers, etc.), and this is often linked to dramatic changes in their physical and chemical properties as compared to the original properties of the isolated units. Dimers and trimers can also be formed in the excited state potential energy surfaces, i.e., excimers. Excimers are short-lived but are also often characterized by different optical properties from those of the isolated units. Understanding the nature of noncovalent interactions and the presence or not of cooperativity effects in both aggregates and excimers is thus extremely important to rationalize these variations. In this study, we present computational investigations on isoquinolinyl pyrazolate Pt(II) complexes. Our results highlight that cooperativity effects between noncovalent interactions, which are modulated by sterically demanding substituents and metallophilic Pt•••Pt interactions, are present only on certain investigated excimers. We use density functional theory (DFT) calculations to examine the cooperativity effects and the changes in the photophysical properties. Different descriptors of cooperativity effects between noncovalent interactions, including the synergetic, genuine nonadditive, and total interaction energies, were evaluated for a series of Pt(II) aggregates and excimers. In addition, energy decomposition analysis (EDA) calculations were performed to rationalize the origins of the cooperative effects. The cooperative effects in trimer excimers (in their lowest triplet excited state, i.e., T 1 ) led to shortened Pt••• Pt contacts as compared to the trimer aggregates. Furthermore, this synergy between noncovalent interactions is ultimately responsible for the formation of the excimers and the striking changes in the measured photophysical properties. More in detail, we report a change in the character of the lowest-lying triplet excited state when going from dimer excimers (i.e., of mixed triplet ligandcentered and triplet metal-to-ligand charge transfer ( 3 LC/ 3 MLCT) character) to trimer excimers (i.e., of triplet metal−metal-toligand charge transfer ( 3 MMLCT) character). The EDA reveals that the total interaction energy on trimer excimers is subtly controlled by the electrostatic and dispersion terms.

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Excimer‐ und Exciplex‐Bildung in durch aurophile Wechselwirkungen präkonditionierten Gold(I)‐ Komplexen

Cited by 3 publications

References 243 publications

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

Formation of Excimers in Isoquinolinyl Pyrazolate Pt(II) Complexes: Role of Cooperativity Effects

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Excimer‐ und Exciplex‐Bildung in durch aurophile Wechselwirkungen präkonditionierten Gold(I)‐ Komplexen

Cited by 3 publications

References 243 publications

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)2]−}n Moieties Generated in d–f Heterometallic Assemblies

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)2]−}n Moieties Generated in d–f Heterometallic Assemblies

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)2]−}n Moieties Generated in d–f Heterometallic Assemblies

Formation of Excimers in Isoquinolinyl Pyrazolate Pt(II) Complexes: Role of Cooperativity Effects

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Product

Resources

About

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies

Ratiometric and Colorimetric Optical Thermometers Using Emissive Dimeric and Trimeric {[Au(SCN)₂]⁻}_n Moieties Generated in d–f Heterometallic Assemblies