Dicesium sodium dicyanoaurate(I), Cs2Na[Au(CN)2]3. Crystal-chemical relationship to potassium dicyanoaurate(I) and -argentate(I)

Blom, Nils; Lüdi, A.; Bürgi, Hans‐Beat

doi:10.1107/s0108270184009483

Cited by 15 publications

(12 citation statements)

References 2 publications

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“…In crystals of the alkali salts (M = Na, K, Rb,Cs), the anions are packed in sheets with all gold atoms in ac ommon plane and with the cyanide groups extending roughly perpendicular from this plane above and below.T he assembly pattern depends on the size of the counterion, and the Au•••Au contacts vary across as mall range around an average of 3.33 . [91][92][93][94][95][96] Figure 1s hows an idealized structure of a{ [Au-(CN) 2 ] n } nÀ sheet with the most common hexagonal array of gold atoms.Asanexample of adistorted variant, in crystals of Rb[Au(CN) 2 ], the gold atoms are arranged in ap lane composed of four-a nd eight-membered rings. [96] Already in many publications of early structural work it has repeatedly been assumed that "there may be significant bonding interactions among the gold atoms in these solids".…”

Section: The Case Of the Dicyanoaurate(i) Anionmentioning

confidence: 99%

Section: Relevant Aspects Of Aurophilic Aui−aui Bondingmentioning

confidence: 99%

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Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Schmidbaur

Raubenheimer

2020

Angew Chem Int Ed

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Excimers and exciplexes are defined as assemblies of atoms or molecules A/A′ where interatomic/intermolecular bonding appears only in excited states such as [A2]* (for excimers) and [AA′]* (for exciplexes). Their formation has become widely known because of their role in gas‐phase laser technologies, but their significance in general chemistry terms has been given little attention. Recent investigations in gold chemistry have opened up a new field of excimer and exciplex chemistry that relies largely on the preorganization of gold(I) compounds (electronic configuration AuI(5d10)) through aurophilic contacts. In the corresponding excimers, a new type of Au⋅⋅⋅Au bonding arises, with bond energies and lengths approaching those of ground‐state Au−Au bonds between metal atoms in the Au0(5d106s1) and AuII(5d9) configurations. Excimer formation gives rise to a broad range of photophysical effects, for which some of the relaxation dynamics have recently been clarified. Excimers have also been shown to play an important role in photoredox binuclear gold catalysis.

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Section: The Case Of the Dicyanoaurate(i) Anionmentioning

confidence: 99%

Section: Relevant Aspects Of Aurophilic Aui−aui Bondingmentioning

confidence: 99%

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Schmidbaur

Raubenheimer

2020

Angew Chem Int Ed

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“…M[Au(CN) 2 ] compounds (e.g., with M + = K + , Cs + , Tl + ) have been the subject of increasing interest due to their two-dimensional layered structures and their interesting emission properties. − These structures consist of layers of [Au(CN) 2 ] - complexes alternating with layers of M + ions, which are in several cases coordinated with water molecules. − The distances between the gold ions within the layers are relatively short and change with the cation M + . For example, the Au + ions are separated by 3.64 Å (at T = 300 K) for the potassium compound, while the shortest Au−Au separation is only 3.11 Å for M = Cs .…”

Section: Introductionmentioning

confidence: 99%

Tunable Radiationless Energy Transfer in Eu[Au(CN)₂]₃·3H₂O by High Pressure

et al. 1998

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The title compound consists of two-dimensional layers of [Au(CN)2]- complexes alternating with layers of Eu3+ ions. Due to this structure type, the lowest electronic transitions of the dicyanoaurates(I) exhibit an extreme red shift of Δν̄max/Δp = −130 ± 10 cm-1/kbar under high-pressure application at least up to ≈60 kbar (T = 20 K), while the shifts of the different Eu3+ transitions lie between −0.70 and −0.94 cm-1/kbar. At ambient pressure, the usually very intense emission of the dicyanoaurates(I) is completely quenched due to radiationless energy transfer to the Eu3+ acceptors. As a consequence, one observes a strong emission from Eu3+, which is assigned to stem mainly from 5D0 but also weakly from 5D1. At T = 20 K, 5D3 seems to be the dominant acceptor term. It is a highlight of this investigation that, with increasing pressure, the emission from the dicyanoaurate(I) donor states can continuously be tuned in by tuning off the resonance condition (spectral overlap) for radiationless energy transfer to 5D3. With further increase of pressure, successively, 5D2 and 5D1 become acceptor terms, however, being less efficient. Interestingly, 5D0 does not act as an acceptor term even with maximum spectral overlap. Between 30 and 60 kbar, when only the 7F0 → 5D1 acceptor absorption overlaps with the donor emission, one finds a linear dependence of the (integrated) 5D0 emission intensity on the spectral overlap integral, as is expected for resonance energy transfer. As the dominant transfer mechanism, the Dexter exchange mechanism is proposed. Besides the high-pressure studies of the Eu3+ line structure at T = 20 K, the Eu3+ emission is also investigated at T = 1.2 K (p = 0 kbar) by time-resolved emission spectroscopy, which strongly facilitates the assignments of the emitting terms.

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“…In Kristallen der Alkalimetall‐Salze (M=Na, K, Rb, Cs) sind die Anionen in Schichten gepackt, wobei alle Goldatome in einer Ebene liegen und die Cyanid‐Gruppen nahezu senkrecht aus dieser Ebene nach oben und unten herausstehen. Das Aggregationsmuster hängt von der Größe der Gegenionen ab, und die Au⋅⋅⋅Au‐Kontakte variieren in einem engen Bereich mit einen Durchschnittswert von 3.33 Å . Abbildung zeigt eine idealisierte {[Au(CN) 2 ] n } n ‐Schicht mit der am häufigsten gefundenen, hexagonalen Anordnung der Goldatome.…”

Section: Relevante Aspekte Der Aurophilen Aui‐aui‐bindungunclassified

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

Schmidbaur

Raubenheimer²

2020

Angewandte Chemie

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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 zugehörigen Excimeren entstehen Au–Au‐Bindungen mit Bindungsenergien und ‐abständen, die denen im Grundzustand von Au0(5d106s1)‐ und AuII(5d9)‐Verbindungen entsprechen. Der aktuelle Kenntnisstand über Excimere und Exciplexe in der Goldchemie wird hier vorgestellt, vorwiegend an einfachen Beispielen wie der Assoziation von [Au(CN)2]−‐Anionen in Festkörpern und in Lösung. Die Excimer‐Bildung führt zu einem breiten Spektrum an photophysikalischen Effekten, deren Relaxationsdynamik in einigen Fällen kürzlich aufgeklärt wurde. Excimere sind aktuell auch von großer Bedeutung auf dem Gebiet der “photoredox binuclear gold catalysis”.

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Dicesium sodium dicyanoaurate(I), Cs2Na[Au(CN)2]3. Crystal-chemical relationship to potassium dicyanoaurate(I) and -argentate(I)

Cited by 15 publications

References 2 publications

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Tunable Radiationless Energy Transfer in Eu[Au(CN)₂]₃·3H₂O by High Pressure

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

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Dicesium sodium dicyanoaurate(I), Cs2Na[Au(CN)2]3. Crystal-chemical relationship to potassium dicyanoaurate(I) and -argentate(I)

Cited by 15 publications

References 2 publications

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Tunable Radiationless Energy Transfer in Eu[Au(CN)2]3·3H2O by High Pressure

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

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Tunable Radiationless Energy Transfer in Eu[Au(CN)₂]₃·3H₂O by High Pressure