Orange Luminescence and Structural Properties of Three Isostructural Halocyclohexylisonitrilegold(I) Complexes

White‐Morris, Rochelle L.; Olmstead, Marilyn M.; Balch, Alan L.; Elbjeirami, Oussama; Omary, Mohammad A.

doi:10.1021/ic0341946

Cited by 73 publications

(67 citation statements)

References 52 publications

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“…The T 1 phosphorescent excited state reveals a large Stokes' shift about 12 000 cm −1 (Figure 2) and lifetimes of 2.55−226 μs (Table S3), providing orange emission as already known in the literature. 15 In contrast, S excited state emits white or pale blue fluorescence with lifetime between 0.17 and 2.76 ns. Although a small contribution of fluorescence from the excimeric interaction in the S 1 excited state could appear in the region beyond λ ex = 370 nm at room temperature, it was difficult to distinguish a high energy emission band formed by Au I ···Au I aurophilic interaction from the background fluorescence of imidazolium cations.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Photophysical Property of catena-Bis(thiocyanato)aurate(I) Complexes in Ionic Liquids

Aoyagi

Shinha

Ikeda‐Ohno

et al. 2015

Crystal Growth & Design

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The photochemistry of a gold(I) thiocyanate complex has been investigated to determine the coordination structure in both the solid and liquid states. The coordination geometries of the supramolecular [Au(SCN) 2 ] n complex and the concomitant exciplex have mainly been analyzed by crystallographic analysis and X-ray absorption spectroscopy. The Au−S bond distance and Au···Au separation of the compound in the S 0 ground state and in the T 1 phosphorescent excited state (λ ex = 340 nm) were compared. Upon irradiation with UV light, the excimeric interactions were enhanced, resulting in a contraction of the Au I ···Au I aurophilic distance by 0.0113(4) Å. A broad luminescence spectrum was observed for the one-dimensional chain suprastructure. The time-resolved luminescence spectra indicated the entity of several oligomeric species in the crude liquid without neutral solvent molecules. In addition, extended X-ray absorption fine structure spectroscopy exhibited a slight change in the nearest Au−S distance due to the photoswitched transformation. The deformation of the (Au---Au)* exciplexes was not apparently promoted in the liquid state with the asymmetrical imidazoium cations having a nonlocal charge distribution in the present observation. This is plausibly due to a flexible molecular structure and a property in the liquid state. In conclusion, the photoexcited nature of the pseudo-one-dimensional complexes has emerged in controlling bond distances among the supramolecular networks.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Photophysical Property of catena-Bis(thiocyanato)aurate(I) Complexes in Ionic Liquids

Aoyagi

Shinha

Ikeda‐Ohno

et al. 2015

Crystal Growth & Design

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“…The versatility of the coordination modes of the heavy metals has enabled wide structure and topology variations of the complexes. The self‐assembly of molecules with gold atoms involves inter‐ and/or intramolecular interactions that lead to the formation of dimers, oligomers, chains, sheets, clusters, and nanoparticles (see Figure ), allowing the generation of systems of high complexity . In addition to the aforementioned noncovalent interactions, metal−metal and representative‐atom‐metal interactions in the complexes have also been found to be associated with the direct formation of this type of self‐assemblies .…”

Section: Dispersion Interactions In Materials Based On Heavy Metalsmentioning

confidence: 99%

Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

Barrientos

Miranda-Rojas

Mendizábal

2018

Int J of Quantum Chemistry

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Complexity is a concept that is being considered in chemistry as it has shown potential to reveal interesting phenomena. Thus, it is possible to study chemical phenomena in a new approach called systems chemistry. The systems chemistry has an organization and function, which are regulated by the interactions among its components. At the simplest level, noncovalent interactions between molecules can lead to the emergence of large structures. Consequently, it is possible to go from the molecular to the supramolecular systems chemistry, which aims to develop chemical systems highly complex through intra-and intermolecular forces. Proper use of the interactions previously mentioned allow a glimpse of supramolecular system chemistry in many tasks such as structural properties reflecting certain behaviors in the chemistry of materials, for example, electrical and optical, processes of molecular recognition and among others. In the last time, within this area, inorganic supramolecular systems chemistry has been developed. Those systems have a structural orientation which is defined by certain forces that predominate in the associations among molecules. It is possible to recognize these forces as hydrogen bonding, π-π stacking, halogen bonding, electrostatic, hydrophobic, charge transfer, metal coordination, and metallophilic interactions. The presence of these forces in supramolecular system yields certain properties such as light absorption and luminescence. The quantum theoretical modeling plays an important role in the designing of the supramolecular system. The goal is to apply supramolecular principles in order to understand the associated forces in many inorganic molecules that include heavy metals for instance gold, platinum, and mercury. Relevant systems will be studied in detail, considering functional aspects such as enhanced coordination of functionalized molecular self-assembly, electronic and optoelectronic properties. K E Y W O R D Sdensity functional theory, dispersion term, Post-Hartree-Fock, van der Waals forces Grimme´s dispersion (D3)

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“…However, a small variation in the complexes such as, for example, in the isocyanide group of the related (RNC)AuX complexes (R ¼ Cy; X ¼ Cl, Br, I, CN)(R ¼ n Bu, i Pr, Cy, Me, t Bu; X = CN), can lead to a different origin of the optical behavior [17,18]. For example, in the case of the halogen derivatives, as in the previous case, the complexes show different supramolecular organization: chains, dimers and isolated molecules.…”

Section: Network From Mononuclear Unitsmentioning

confidence: 99%

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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Orange Luminescence and Structural Properties of Three Isostructural Halocyclohexylisonitrilegold(I) Complexes

Cited by 73 publications

References 52 publications

Photophysical Property of catena-Bis(thiocyanato)aurate(I) Complexes in Ionic Liquids

Photophysical Property of catena-Bis(thiocyanato)aurate(I) Complexes in Ionic Liquids

Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

Luminescence of Supramolecular Gold‐Containing Materials

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