Tunable Photoluminescence of Closed-Shell Heterobimetallic Au−Ag Dicyanide Layered Systems

Colis, Julie Clarissa F.; Larochelle, Christie; Fernández, Eduardo J.; López‐de‐Luzuriaga, José M.; Monge, Miguel; Laguna, Antonio; Tripp, Carl P.; Patterson, Howard H.

doi:10.1021/jp045868g

Cited by 42 publications

(35 citation statements)

References 59 publications

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“…This was the case for the silver-gold mixed metal systems of stoichiometry M[Ag x Au 1Àx (CN) 2 ] 3 Á3H 2 O (M ¼ La [59], Eu [60]) obtained and studied by the same group, and which exhibited tunable photoluminescence depending on the Au/Ag stoichiometric ratio in the complexes. However, with this anion, in addition to the possibility of using both donor atoms of the cyanide group, the gold center can itself act as a donor, since the negative charge of each cyanide ligand increases the electronic density on this metal, making it a potential donor center.…”

Section: Luminescent Supramolecular Gold-heterometal Entities J377mentioning

confidence: 87%

Luminescence of Supramolecular Gold‐Containing Materials

López‐de‐Luzuriaga

2008

Modern Supramolecular Gold Chemistry

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In addition to the characteristics that make gold a unique element, such as the lowest electrochemical potential of all metals, its high electronegativity, or the fact that it may have a mononegative oxidation state, perhaps the most intriguing characteristic is the tendency of many gold complexes to aggregate into oligomers or supramolecular assemblies through metal-metal interactions. This fact, far from being a chemical curiosity, has become an object of study because of the associated properties. One of the most studied properties and that which involves many groups all over the world is the luminescence displayed by many gold-containing complexes. In fact, after the discovery of the luminescence of the three-coordinate complex [AuCl(PPh 3 ) 2 ] by Dori and coworkers in 1970 [1], the number of groups that have studied this topic has increased rapidly in recent years, together with the number of synthesized luminescent gold molecules. At the same time, the large number of studies performed in this area has provided knowledge of the conditions that gold complexes require to display luminescence. For instance, luminescence can originate from ligands, assigned to certain geometries around the gold atom or from the presence of metal-metal interactions in the complexes. More specifically, it can be produced by transitions between orbitals of the metal center exclusively, in orbitals of the ligands, usually among p orbitals, or in transitions involving both metal and ligands, where these can act as donors or acceptors of electronic density (charge transfer transitions). In gold (I), with a d 10 closed shell configuration, the ground state is 1 S 0 , while the excited states are 3 D 2 , 3 D 1 , 3 D 0 and 1 D 0 (see Figure 6.1) [2].Of all these, the only permitted electronic transition is 1 D 0 1 S 0 , while the rest are forbidden according to the spin rule, leading to phosphorescent emissions. However, these are precisely the ones responsible for the emissions found in many luminescent gold complexes, appearing in a range between 500 and 700 nm (665 nm in the gaseous ion). j347Another very important factor that should be considered is the expected large spin-orbit effect promoted by a heavy atom such as gold. This effect produces a relaxation of the spin rule and makes orbital forbiddenness instead of the spin rule the key factor for determining whether a gold complex will show luminescence. For instance, phosphorescence is generally not observed for linear molecules (where the ligands are not involved in the transitions), since the mixing of s, p z and d z 2 of gold form a HOMO of S þ symmetry, while the LUMO orbital is formed mainly from p x and p y leading to a P symmetry, consequently, there is no orbital forbiddenness in the transition and phosphorescence is not observed [3]. Another possible coordination environment at gold is the tetrahedral one. In that case, the HOMO and the LUMO are 1 T 2 in symmetry and the transition is allowed according to Laportes rule; therefore, phosphorescence is not observed in thes...

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Section: Luminescent Supramolecular Gold-heterometal Entities J377mentioning

confidence: 87%

Luminescence of Supramolecular Gold‐Containing Materials

López‐de‐Luzuriaga

2008

Modern Supramolecular Gold Chemistry

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“…Since these crystals are not soluble in water or other common solvents, a determination of the exact ratio requires an analysis by X-ray diffraction. We have determined the exact ratio in several other crystals of this type and found them to be close to the ratios in the starting solution [14].…”

Section: Methodsmentioning

confidence: 59%

“…It has been proposed that the donor states in the pure silver and gold crystals are long lived triplet states that are spatially localized due to cluster formation in the metal layers. In contrast, the unique emission properties in the mixed systems have been well explained by delocalization of the excited states over the silver and gold atoms [15,14]. This delocalization allows for the possibility of rapid energy migration along the silver-gold layer.…”

Section: Article In Pressmentioning

confidence: 99%

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Tunable excited state energy transfer in [

Larochelle

Seemuller

2008

Journal of Luminescence

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“…Like their oxide and cyanide cousins, dicyanometallate frameworks exhibit a variety of important functional responses. Examples include colossal positive and negative thermal expansion in silver hexacyanocobaltate (≡Co III [Ag I (CN) 2 ] 3 ); 12 giant negative compressibility and guest-dependent luminescence in Zn[Au(CN) 2 ] 2 ; 13 , 14 piezoelectric behavior in KCo[Au(CN) 2 ] 3 ; 15 tunable room-temperature luminescence in La[Au x Ag 1– x (CN) 2 ]·3H 2 O; 16 vapochromism in Cu[Au(CN) 2 ] 2 ; 17 heat-, light-, and pressure-induced spin-crossover in Fe(pyz)[Ag(CN) 2 ] 2 ·pyz (pyz = pyrazine); 18 and strain-free charge storage in K x Fe II/III [Ag(CN) 2 ] 3 . 19 In each of these cases, the geometric flexibility of the dicyanometallate linker plays a key role and so there is good reason to expect similarly intriguing functional responses among as-yet-unrealised dicyanometallate frameworks.…”

Section: Introductionmentioning

confidence: 99%

Dicyanometallates as Model Extended Frameworks

2016

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We report the structures of eight new dicyanometallate frameworks containing molecular extra-framework cations. These systems include a number of hybrid inorganic–organic analogues of conventional ceramics, such as Ruddlesden–Popper phases and perovskites. The structure types adopted are rationalized in the broader context of all known dicyanometallate framework structures. We show that the structural diversity of this family can be understood in terms of (i) the charge and coordination preferences of the particular metal cation acting as framework node, and (ii) the size, shape, and extent of incorporation of extra-framework cations. In this way, we suggest that dicyanometallates form a particularly attractive model family of extended frameworks in which to explore the interplay between molecular degrees of freedom, framework topology, and supramolecular interactions.

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Tunable Photoluminescence of Closed-Shell Heterobimetallic Au−Ag Dicyanide Layered Systems

Cited by 42 publications

References 59 publications

Luminescence of Supramolecular Gold‐Containing Materials

Luminescence of Supramolecular Gold‐Containing Materials

Tunable excited state energy transfer in [

Dicyanometallates as Model Extended Frameworks

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