[Au2(μ-G)(μ-dmpe)]·(KBr)0.75·2H2O, a cyclic dinuclear gold(I) complex with an N3,N9-bridging coordination mode of guanine and aurophilic interactions: synthesis, X-ray crystal structure and luminescence properties (dmpe=1,2-bis(dimethylphosphino)ethane and G=guaninato dianion)

Colacio, Enrique; Crespo, Olga; Cuesta, Rafael; Kivekäs, Raikko; Laguna, Antonio

doi:10.1016/j.jinorgbio.2004.01.013

Cited by 13 publications

(12 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is observed that, as the other systems presented in this work, the 6s and 6p orbitals are partially filled, whereas the 5d shell is broken. No intermolecular interactions are found at this level of theory for compound (3), in agreement with the experimental results reported by Colacio et al [22].…”

Section: Electronic Structuresupporting

confidence: 92%

“…The computed NBO charges are reported in Table VI for the isolated complex 3 and with the presence of the Br atom, as it was experimentally reported, i.e., [Au 2 (l-G)(l-dmpe)] Br [22]. The electronic charge at the Au1 atom appears to be unchanged because no interaction is present with adjacent atoms.…”

Section: Electronic Structurementioning

confidence: 80%

“…6 found through experiments. On the other hand, K þ and O À ions, located about the (l-dmpe) ligand, as well as the water molecules within the complex [[Au 2 (l-G)(ldmpe)](KBr)0.75 2H 2 O] have been omitted for its study because it is known that they have no influence on its luminescent properties [22]. Hence, the resulting system [Au 2 (l-G)(l-dmpe)] (complex 3) was fully optimized at the MP2 level.…”

Section: Structural Descriptionmentioning

confidence: 99%

“…This complex has been recently synthesized by Colacio et al [22], and it is characterized by a metal-guanine bonding. The understanding of the mechanism governing such bonding and its possible relation with the phosphorescent behavior is of high relevance.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Effects of the Au(I)–Au(I) closed‐shell attraction on the electronic and phosphorescent properties in a series of coordination compounds: A theoretical study

Muñiz

Sansores

Reyes-Nava

et al. 2011

Int J of Quantum Chemistry

View full text Add to dashboard Cite

ABSTRACT:The Au(I)-Au(I) closed-shell or aurophilic attraction has been the subject of interest in the experimental and theoretical chemistry fields, due to the intriguing properties associated to it. The presence of phosphorescence in ''aurophilic'' compounds has been addressed to a wide range of applications, but it has not yet been fully understood. A theoretical study on the electronic and phosphorescent properties of the following series of dinuclear gold complexes has been performed: [Au 2 (dmpm) (i-mnt)] (1), [Au 2 (l-Me-TU) (l-dppm)] (2), and [Au 2 (l-G)(l-dmpe)] (3). Full geometry optimizations at the second-order Møller-Plesset perturbation theory (MP2) were carried out for each of the species. These calculations made evident that, at the groundstate geometry, the Au(I) cations allocated at the center of the ring show a short Au-Au distance below the sum of the van der Waals radii, at the range of the aurophilic attraction. An intermolecular Au(I)-Au(I) closed-shell attraction for a pair of the systems under study is found. This attraction is comparable to that of the hydrogen bonds. The phosphorescent properties experimentally observed for this series were also characterized through ab initio techniques. The obtained results allow to fit reasonably

show abstract

Section: Electronic Structuresupporting

confidence: 92%

Section: Electronic Structurementioning

confidence: 80%

Section: Structural Descriptionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Effects of the Au(I)–Au(I) closed‐shell attraction on the electronic and phosphorescent properties in a series of coordination compounds: A theoretical study

Muñiz

Sansores

Reyes-Nava

et al. 2011

Int J of Quantum Chemistry

View full text Add to dashboard Cite

show abstract

“…[Au(3,5-Ph 2 pz)(dppp)] [35], [Au 2 (G)(dmpe)] (G ¼ guaninato dianion; dmpe ¼ 1,2-bis(dimethylphosphino)ethane) [293] or the xantine derivatives [Au 2 (HX)(dmpe)], [Au 2 (H 2 TT)(dmpe)] (H 3 X ¼ xantine; H 2 TT ¼ 1,3-dimethyl-8-thioxantine) [294] are examples of dinuclear gold species in which different bidentate ligands bridge both gold atoms in discrete structures with an intranuclear aurophilic interaction. The Xray structure of the luminescent [Au 2 (G)(dmpe)] compound (Figure 2.55a) shows an infrequent N3, N9 bridging mode coordination for guanine.…”

Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

Self Cite

View full text Add to dashboard Cite

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

show abstract

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au₂, {Au₂Ag}_n and {Au₂Cu}_n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

Frik

Jiménez

Gracia

et al. 2012

Chemistry A European J

View full text Add to dashboard Cite

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au2(mes)2(μ-LL)] (LL = dppe: 1,2-Bis(di-phenylphosphano)ethane 1a, and water-soluble dppy: 1,2-Bis(di-3-pyridylphosphano)ethane 1b) with Ag+ and Cu+ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au2M(μ-mes)2(μ-LL)]A (M = Ag, A = ClO4−, L-L = dppe 2a, dppy 2b; M = Ag, A = SO3CF3−, L-L = dppe 3a, dppy 3b; M = Cu, A = PF6−, L-L = dppe 4a, dppy 4b). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au2(mes)2(μ-dppy)] 1b and [Au2Ag(μ-mes)2(μ-dppe)]SO3CF3 3a were determined by a single-crystal X-ray diffraction study. 3a in solid state is not a cyclic trinuclear Au2Ag derivative but it gives an open polymeric structure instead, with the {Au2(μ-dppe)} fragments “linked” by Ag(μ-mes)2 units. The very short distances of 2.7559(6) Å (Au-Ag) and 2.9229(8) Å (Au-Au) are indicative of gold-silver (metallophillic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self-aggregation of [Au2M(μ-mes)2(μ-LL)]+ units (M= Ag or Cu; LL= dppe or dppy) into an extended chain structure, through Au-Au and/or Au-M metallophylic interactions, as that observed for 3a. In solid state the heterometallic Au2M complexes with dppe (2a–4a) show a shift of emission maxima (from ca. 430 to the range of 520–540 nm) as compared to the parent dinuclear organometallic product 1a while the complexes with dppy (2b–4b) display a more moderate shift (505 for 1b to a max of 563 nm for 4b). More importantly, compound [Au2Ag(μ-mes)2(μ-dppy)]ClO4 2b resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au2Cl2(μ-LL)] (L-L dppy 5b) was also studied for comparative purposes. The antimicrobial activity of 1–5 and AgA (A= ClO4−, OSO2CF3−) against Gram-positive and Gram-negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au2M derivatives with dppe (2a–4a) were the more active (MIC 10 to 1 μg/mL). Compounds containing silver were ten times more active to Gram-negative bacteria than the parent dinuclear compound 1a or silver salts. Au2Ag compounds with dppy (2b, 3b) were also potent against fungi.

show abstract

[Au2(μ-G)(μ-dmpe)]·(KBr)0.75·2H2O, a cyclic dinuclear gold(I) complex with an N3,N9-bridging coordination mode of guanine and aurophilic interactions: synthesis, X-ray crystal structure and luminescence properties (dmpe=1,2-bis(dimethylphosphino)ethane and G=guaninato dianion)

Cited by 13 publications

References 35 publications

Effects of the Au(I)–Au(I) closed‐shell attraction on the electronic and phosphorescent properties in a series of coordination compounds: A theoretical study

Effects of the Au(I)–Au(I) closed‐shell attraction on the electronic and phosphorescent properties in a series of coordination compounds: A theoretical study

Gold–Gold Interactions

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au₂, {Au₂Ag}_n and {Au₂Cu}_n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

Contact Info

Product

Resources

About

[Au2(μ-G)(μ-dmpe)]·(KBr)0.75·2H2O, a cyclic dinuclear gold(I) complex with an N3,N9-bridging coordination mode of guanine and aurophilic interactions: synthesis, X-ray crystal structure and luminescence properties (dmpe=1,2-bis(dimethylphosphino)ethane and G=guaninato dianion)

Cited by 13 publications

References 35 publications

Effects of the Au(I)–Au(I) closed‐shell attraction on the electronic and phosphorescent properties in a series of coordination compounds: A theoretical study

Effects of the Au(I)–Au(I) closed‐shell attraction on the electronic and phosphorescent properties in a series of coordination compounds: A theoretical study

Gold–Gold Interactions

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au2, {Au2Ag}n and {Au2Cu}n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

Contact Info

Product

Resources

About

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au₂, {Au₂Ag}_n and {Au₂Cu}_n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents