Dinuclear Gold(I) Chloride Complexes with Diarsine Ligands

Kobayashi, Ryosuke; Fujii, Tomoki; Imoto, Hiroaki; Naka, Kensuke

doi:10.1002/ejic.202000810

Cited by 10 publications

(8 citation statements)

References 40 publications

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“…Naka and co-workers have done elegant work on 2arylbenzo[b]arsole derivatives and studied their photo-luminescence properties in detail. The same group reported 2,3diarylbenzo[b] arsoles (61)(62)(63)(64)(65)(66)(67)(68)(69)(70) by taking advantage of zirconocene based synthetic methods. 2,3-Diarylbenzo[b] arsoles 61-67 were synthesized according to the procedures described in Scheme 12.…”

Section: 3-diarylbenzo[b]arsole (Dabza)mentioning

confidence: 99%

“…In this direction, Naka and Imoto utilized various kinds of diarsenic ligands (diars=dpae, dpap, dpab, cis ‐dpav, trans ‐dpav, dpapz, and dpaq) [63] for the synthesis of Au complexes of the type [Au 2 Cl 2 (diars)]. By following the elegant method for the preparation of arsenic nucleophile (Scheme 1; method b) the authors generated diphenylarsanyllithium (Ph 2 AsLi) from the reaction of hexaphenylhexaarsine (As 6 Ph 6 ) with phenyl lithium, which on further treatment with alkyl, vinyl, or aryl dichlorides afforded corresponding bidentate ligands ( 15 – 21 ) as shown in Scheme 3.…”

Section: Synthetic Strategies For the Preparation Of Organoarsenic Co...mentioning

confidence: 99%

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Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

et al. 2023

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Recent success in the synthesis of π-conjugated heavier pnictogen (As, Sb, and Bi) compounds and their transition metal complexes has led to the current surge in interest that led to significant development in the field of photophysical and optoelectronic properties of heavier pnictogens and their transition metal complexes. The presence of heavier pnictogens (As, Sb and Bi) in the molecular skeleton promotes inter-system crossing (ISC) and reverse inter-system crossing (RISC), because of the heavy atom effect, via altering the intermolecular interactions and orbital energy levels. As a result, π-conjugated heavier pnictogen compounds such as arsines, dibenzoarsepins, arsinoquinoline, heterofluorene, benzo[b]heterole (heterole = arsole, bismole, and stibole) show unique optoelectronic properties such as narrow bandgap, low-energy absorption, and long-wavelength emission than lighter pnictogen-based compounds. This review focuses on recent advances in the synthesis and photophysical properties of heavier pnictogen compounds. The synthesis and photophysical properties of heavier pnictogens are discussed and elaborated.

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Section: 3-diarylbenzo[b]arsole (Dabza)mentioning

confidence: 99%

Section: Synthetic Strategies For the Preparation Of Organoarsenic Co...mentioning

confidence: 99%

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

et al. 2023

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“…The angular features shown in Figure 13 c,d and f indicate that the As···N, As···O and As···As intramolecular contacts are quasi-linear in the phenyl diquinoline complex (CSD ref. code CACXEN) [ 193 ], the keto arsenic ylid (BOTLUR01) [ 194 ], and the diarsine complex (EJABID) [ 195 ]. The contacts are shorter than the sum of the vdW radii of the respective atomic basins.…”

Section: Arsenic In Crystalsmentioning

confidence: 99%

“…( c , d ) Histograms showing the distribution of 64 As···N contacts and ∠R–As···N in 43 crystals emerged from a CSD search, with the normal distribution curve in red. Illustration of inter- and intramolecular arsenic bonds in some crystals catalogued in the CSD, including: ( e ) 8,8′-(phenylarsanediyl)diquinoline [ 193 ]; ( f ) 1-phenyl-2-(triphenyl-arsanylidene)ethan-1-one [ 194 ]; ( g ) triphenyl(ethoxycarbonylmethyl)arsonium tri-iodide [ 196 ]; ( h ) 2,3-bis(diphenylarsino)pyrazine [ 195 ]; ( i ) tetraphenylarsonium trifluoroacetylide-dicyanomethanide [ 197 ]; ( j ) diazido-chloro-pyridyl-arsenic(III) [ 198 ]. Selected bond lengths and angles are shown in Å and degree, respectively.…”

Section: Arsenic In Crystalsmentioning

confidence: 99%

The Pnictogen Bond: The Covalently Bound Arsenic Atom in Molecular Entities in Crystals as a Pnictogen Bond Donor

Varadwaj

Marques

et al. 2022

Molecules

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In chemical systems, the arsenic-centered pnictogen bond, or simply the arsenic bond, occurs when there is evidence of a net attractive interaction between the electrophilic region associated with a covalently or coordinately bound arsenic atom in a molecular entity and a nucleophile in another or the same molecular entity. It is the third member of the family of pnictogen bonds formed by the third atom of the pnictogen family, Group 15 of the periodic table, and is an inter- or intramolecular noncovalent interaction. In this overview, we present several illustrative crystal structures deposited into the Cambridge Structure Database (CSD) and the Inorganic Chemistry Structural Database (ICSD) during the last and current centuries to demonstrate that the arsenic atom in molecular entities has a significant ability to act as an electrophilic agent to make an attractive engagement with nucleophiles when in close vicinity, thereby forming σ-hole or π-hole interactions, and hence driving (in part, at least) the overall stability of the system’s crystalline phase. This overview does not include results from theoretical simulations reported by others as none of them address the signatory details of As-centered pnictogen bonds. Rather, we aimed at highlighting the interaction modes of arsenic-centered σ- and π-holes in the rationale design of crystal lattices to demonstrate that such interactions are abundant in crystalline materials, but care has to be taken to identify them as is usually done with the much more widely known noncovalent interactions in chemical systems, halogen bonding and hydrogen bonding. We also demonstrate that As-centered pnictogen bonds are usually accompanied by other primary and secondary interactions, which reinforce their occurrence and strength in most of the crystal structures illustrated. A statistical analysis of structures deposited into the CSD was performed for each interaction type As···D (D = N, O, S, Se, Te, F, Cl, Br, I, arene’s π system), thus providing insight into the typical nature of As···D interaction distances and ∠R–As···D bond angles of these interactions in crystals, where R is the remainder of the molecular entity.

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“…Arsines have widely been used as alternative ligands to phosphines for various metal complexes because of similar chemical properties of phosphorus and arsenic. [23][24][25] However, they have been rarely used for the protection of gold clusters, 26,27 and no examples of diarsine-protected gold clusters have been reported. In this paper, we report the synthesis, characterization, single-crystal x-ray diffraction structure, and optical properties of novel diarsine-protected [Au 13 L5Cl 2 ] 3+ -type clusters and discuss the effects of arsenic ligands on the geometric and electronic structures in comparison with the phosphino analogs.…”

Section: Introductionmentioning

confidence: 99%

Diarsine- vs diphosphine-protected Au13 clusters: Effect of subtle geometric differences on optical property and electronic structure

Shichibu

Zhang

Chen

et al. 2021

The Journal of Chemical Physics

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In the design of ligand-protected metal clusters, the choice of protecting ligands is a critical factor because they can profoundly affect the nuclearity, geometry, and electronic structures to afford a diverse range of cluster compounds. Here, we report the synthesis of two novel diarsine-protected Au 13 clusters ([Au 13 L5Cl 2 ] 3+ , L = diarsine) and compare these clusters with diphosphine analogs in terms of the core geometry and optical properties. In the crystal structure, the cluster bearing C3-bridged diarsines {[Au 13 (dpap)5Cl 2 ] 3+ , 3} had an apparently identical icosahedral Au 13 core to [Au 13 (dppe)5Cl 2 ] 3+ (1) with C2-bridged diphosphines, but slight structural differences associated with the bridging unit of the ligands were found. Despite similar icosahedral Au 13 cores 1 and 3, their absorption and photoluminescence profiles were evidently different. Theoretical calculations revealed that the subtle deformation of the Au 13 icosahedron, rather than the coordinating atoms (As or P), notably influences the electronic structure to cause the difference in the absorption profiles.

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Dinuclear Gold(I) Chloride Complexes with Diarsine Ligands

Cited by 10 publications

References 40 publications

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

The Pnictogen Bond: The Covalently Bound Arsenic Atom in Molecular Entities in Crystals as a Pnictogen Bond Donor

Diarsine- vs diphosphine-protected Au13 clusters: Effect of subtle geometric differences on optical property and electronic structure

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