Emission Energy Correlates with Inverse of Gold−Gold Distance for Various [Au(SCN)<sub>2</sub>]<sup>-</sup> Salts

Coker, Nathan L.; Bauer, Jeanette A. Krause; Elder, R. C.

doi:10.1021/ja037012f

Cited by 137 publications

(112 citation statements)

References 5 publications

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“…Figure 4 A,i, the additional peaks in the XRD spectrum are ascribed to crystalline Au I assembled through aurophilic interactions. [ 27 ] Consistent with the XPS results in Figure 4 A, the XRD pattern recorded after plasma treatment displays refl ections corresponding to pure metallic gold (Figure 4 B,ii). Together, the spectroscopy data in Figure 4 point to spontaneous crystallization and reduction of gold ions, resulting in deposition of crystalline metallic Au 0 through incubation of the Au(SCN) 4 − / DMF/water solution.…”

Section: Introductionsupporting

confidence: 85%

Single‐Step Assembly of Large‐Area, Transparent Conductive Patterns Induced Through Edge Adsorption of Template‐Confined Au‐Thiocyanate

Yin

Mogiliansky

Jelinek

2014

Adv Materials Inter

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been applied for creating microscale surface organization.[ 8 ] Related metal patterning technologies based upon evaporationinduced self-alignment, [9][10][11] direct laser sintering, [12][13][14] and micro-(or nano-) transfer molding have been also reported. [15][16][17][18][19][20][21] However, these techniques also generally require that metallic nanostructures (i.e., nanorods, nanowires, etc.) are prepared prior to surface deposition and patterning. Methodologies combining top-down and bottom-up approaches have been also introduced. [ 22 ] We present a novel, versatile "chemical lithography" strategy for fabricating largearea, organized conductive gold micropatterns. The technology employs a simple single-step process in which a gold complex undergoes slow crystallization/reduction in a confi ned environment. Specifi cally, we demonstrate that diverse patterns of well-defi ned, uniform Au microwires are spontaneously formed through incubation of gold thiocyanate [Au(SCN) 4 − ] dissolved in an organic-solvent/water mixture within confi ned spaces at the interface between polymer molds and surfaces underneath them. The patterning technology is generic in nature as Au organization is only determined by the mold employed. Importantly, the entire patterning process-Au reduction and crystallization, control of microwire size, shape, and organization-occurs spontaneously without any nanostructure pre-synthesis steps. Furthermore, neither stabilizing or shape-directing ligands, nor reducing agents are required for assembly of the Au patterns, as the reducing electrons originate from the thiocyanate ligands. The Au microwires are electrically conductive and produce optically transparent surfaces, pointing for practical uses of the technology as a platform for creation of diverse optoelectronic assemblies and devices. Results and DiscussionThe experimental scheme is illustrated in Figure 1 . An organicsolvent/water solution containing KAu(SCN) 4 is spread upon a solid substrate (Figure 1 A). A polydimethylsiloxane (PDMS) mold having pre-designed pattern is then placed upon the fi lm, effectively confi ning the Au(SCN) 4 − solution into the spaces determined by the stamp (Figure 1 B). Incubation of the gold complex solution within the confi ned areas prevents rapid evaporation of the solvent mixture, instead resulting in slow deposition of Au microwires following crystallization and reduction of the Au 3+ ions by the thiocyanate residues. Recent studies have shown that

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Section: Introductionsupporting

confidence: 85%

Single‐Step Assembly of Large‐Area, Transparent Conductive Patterns Induced Through Edge Adsorption of Template‐Confined Au‐Thiocyanate

Yin

Mogiliansky

Jelinek

2014

Adv Materials Inter

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“…In a few cases such as the luminescence from [Au I (SCN) 2 ] -some trends like those seen in Fig. 28 are readily apparent [51], and the significance of localized pairs of emitting centers revealed [73]. In other cases such as solvoluminescence and the effects of grinding, further detailed understanding of the nature of the emitting sites would be welcome.…”

Section: Discussionmentioning

confidence: 90%

Remarkable Luminescence Behaviors and Structural Variations of Two-Coordinate Gold(I) Complexes

Balch

2007

Photofunctional Transition Metal Complexes

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“…Although association of ions of like charges is not expected it has been observed, indicating that aurophilic interactions may overrule coulombic repulsions. Aggregation of anions is observed in [Au(SCN) 2 ] À [51,52]. A series of salts of the anion [Au(SCN) 2 ] À exhibits different structural features depending on the cation.…”

Section: Dinuclear Aggregatesmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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This chapter focuses mainly on closed shell gold(I) atoms which are found to feel attraction among themselves. This attraction is able to modify expected geometries or support one-, two-or three-dimensional arrays and also leads to interesting properties. Closed shell metal cations are expected to repel each other. Nevertheless, an important number of examples containing [d 8 -d 10 -s 2 ] interactions are known. Particularly strong evidence has been accumulated on the attraction between two or more d 10 shells. In the case of gold(I) such attraction between two or more monovalent gold(I) ions in compounds has been observed structurally for a long time. In these situations the gold centers approach each other to a distance of between 2.7 and 3.3 Å. This range includes the distance between gold atoms in gold metal and approaches, or even overlaps with the range of distances found in the few real Au-Au single bonds. Schmidbaur coined the name aurophilic attraction in 1990 and defined it as the unprecedented affinity between gold atoms even with closed-shell electronic configurations and equivalent electrical charges [1]. Since that moment, aurophilicity has become one of the hot topics in gold chemistry, at first with the aim of understanding such interaction, more recently because of the observation that it may play an important role in interesting properties, thus understanding and modulating aurophilic interactions could help to govern these properties, which include the optical behavior. Although different origins are possible for the luminescent emissions of coordination complexes, such as intraligand transitions (ILT), ligand to metal or metal to ligand charge transfer transitions (LMCT, MLCT) and metal centered (MCT) transitions, in many luminescent gold complexes the emissions have been related to the presence of aurophilic interactions.Information about aurophilicity and chemical situations in which it is observed may be found in different works that may be classified as those which analyse closed shell interactions in general [2], those focused on aurophilicity [1,3], and others which analyze the role of these interactions in coordination [4] and organometallic gold Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna

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Emission Energy Correlates with Inverse of Gold−Gold Distance for Various [Au(SCN)₂]^- Salts

Cited by 137 publications

References 5 publications

Single‐Step Assembly of Large‐Area, Transparent Conductive Patterns Induced Through Edge Adsorption of Template‐Confined Au‐Thiocyanate

Single‐Step Assembly of Large‐Area, Transparent Conductive Patterns Induced Through Edge Adsorption of Template‐Confined Au‐Thiocyanate

Remarkable Luminescence Behaviors and Structural Variations of Two-Coordinate Gold(I) Complexes

Gold–Gold Interactions

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Emission Energy Correlates with Inverse of Gold−Gold Distance for Various [Au(SCN)2]- Salts

Cited by 137 publications

References 5 publications

Single‐Step Assembly of Large‐Area, Transparent Conductive Patterns Induced Through Edge Adsorption of Template‐Confined Au‐Thiocyanate

Single‐Step Assembly of Large‐Area, Transparent Conductive Patterns Induced Through Edge Adsorption of Template‐Confined Au‐Thiocyanate

Remarkable Luminescence Behaviors and Structural Variations of Two-Coordinate Gold(I) Complexes

Gold–Gold Interactions

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Emission Energy Correlates with Inverse of Gold−Gold Distance for Various [Au(SCN)₂]^- Salts