Synthesis and characterization of CuI/AuI complexes derived from monothiocarbonate and tertiary phosphine ligands

Cyue, Jhih-Yu; Kishore, P. R. S.; Liao, Jian‐Hong; Lin, Yung‐Song; Liu, C.W.

doi:10.1016/j.ica.2017.03.018

Cited by 5 publications

(6 citation statements)

References 88 publications

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“…The emission spectrum of 2 showed a sharp peak at 480 nm when excited at 400 nm (this was the excitation maximum observed when emission at 480 nm was studied), and shoulder peaks at ~520 nm and 600 nm. The mononuclear complexes [Au{S(O)CO i Pr}(PPh3)2] and [Au{S(O)CO i Bu}(PPh3)2] showed emission maxima at 462 nm and 471 nm, respectively [21]. The emission peak at 480 nm was therefore tentatively attributed to metal-centred and LMCT transitions.…”

Section: The Gold(i) Complex [Au2{s(o)co I Pr}2(dppe)]nmentioning

confidence: 96%

“…In 2017, two gold(I) monothiocarbonate complexes [Au{S(O)COR}(PPh3)2] (R = i Pr, i Bu) were reported [21]. Both complexes were mononuclear with distorted trigonal planar Au(I) centres, and the monothiocarbonate ligands adopted a monodentate μ-S coordination mode.…”

Section: The Gold(i) Complex [Au2{s(o)co I Pr}2(dppe)]nmentioning

confidence: 99%

“…In this study we focused on silver(I) and gold(I) centers and their reaction with monothiocarbonates. Prior to this study, no silver(I) complex and only two gold(I) complexes containing the monothiocarbonate ligand have been structurally characterized and reported [21].…”

Section: Introductionmentioning

confidence: 99%

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Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

2022

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The monothiocarbonate ligand, [S(O)COR]−, is unusual and rare regarding its use in the formation of coordination compounds. Here, we report the synthesis and structures of the silver(I) and gold(I) monothiocarbonate complexes, [{Ag4(SC(O)OiPr)2(2,2′-bpy)4}(PF6)2]n (1) and [Au2{S(O)COiPr}2(dppe)]n (2), respectively. Both complexes are coordination polymers, with 1 being cationic and 2 neutral. The uniqueness of the ligand is that it is monoanionic and contains both a ‘hard’ O-donor ligand and a ‘soft’ S-donor ligand in a O-C-S manifold with, in principle, electron delocalization across the three atoms. However, for both complexes 1 and 2, it was found that the binding occurred exclusively through the S-donor atom, while the C=O portion remained dangling and was not involved in bonding. This bonding mode departs significantly from the symmetrical S-C-S type ligand such as dithiocarbamates. The structures were analysed and confirmed by NMR and X-ray crystallography.

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Section: The Gold(i) Complex [Au2{s(o)co I Pr}2(dppe)]nmentioning

confidence: 96%

Section: The Gold(i) Complex [Au2{s(o)co I Pr}2(dppe)]nmentioning

confidence: 99%

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Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

2022

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“…[20a] Other similar complexes are the monothiocarbonate complexes [Au{S(O)CO i Pr}(PPh 3 ) 2 ] and [Au{S(O)CO i Bu}(PPh 3 ) 2 ] which are not emissive in solution. The weak blue-green emission observed in the solid state at room temperature is increased at 77 K. [52] The mechanochromic blue emissive mononuclear [Au-(nixantphos)(SCN)] leads, upon grinding, to the red emissive dinuclear ionic compound [Au(nixantphos)] 2 (SCN) 2 . This transformation is reversible upon exposition of [Au-(nixantphos)] 2 (SCN) 2 to ethanol vapors.…”

Section: Complexes With E = S Donor Atommentioning

confidence: 99%

Versatile Emissive Three‐Coordinated Gold(I) Systems‐Properties and Perspectives

2021

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Trigonal planar coordination at gold allows phosphorescent 3 MC transitions, not expected for luminescent mononuclear linear gold complexes. The careful selection and nature of the ancillary ligands bonded to gold, being fluorophore groups or not emissive ligands may cause a distortion of ideal trigonal planar coordination favoring different origins for the emissions. Consequently, intraligand (IL) or charge transfer (CT) transitions may be present and besides the expected phosphorescent MC transitions, fluorescence or thermally activated delayed fluorescence (TADF) may be the origin of the luminescence. In addition of the advantages of triplet population and deactivation via phosphorescent or delayed fluorescence processes, these systems are very versatile and may show interesting properties such as mechanochromism and vapochromism and, consequently, have revealed as promising candidates for optical applications. The objective of this review is to provide an overview of the reported luminescent three-coordinated gold systems and to get insight into their emissive properties.

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“…Such systems are targeted due to their combined potential of large cluster formation and rich photochemistry. 20,21,22 There are only a few complexes known with the monothiocarbonate exhibit non-wheel and mononuclear structures, including iron, 23 manganese, 24 tungsten, 25 ruthenium, 26 zinc, 27 cadmium, 27 copper, 28 and gold 28 complexes. Wheel structures reported for S/O-systems are restricted to the group 11 metals (Cu, Ag, Au) and contain mainly hard O-donor ligands; metal wheels containing S-donor ligands are few and of lower nuclearity.…”

Section: Introductionmentioning

confidence: 99%

[Cu{SC(O)OⁱPr}]₉₆: A Giant Self-Assembled Copper(I) Supramolecular Wheel Exhibiting Photoluminescence Tuning and Correlations with Dynamic Solvation and Solventless Synthesis

et al. 2021

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The hierarchical self-organization of structurally complex high-nuclearity metal clusters with metallosupramolecular wheel architectures that are obtained from the self-assembly of smaller solvated cluster units is rare and unique. Here, we use the potentially heteroditopic monothiocarbonate ligand and demonstrate for the first time the synthesis and structure of a solvated non-cyclic hexadecanuclear cluster [Cu{SC(O)O i Pr}]16·2THF (1) that can simultaneously desolvate and self-assemble in solution and subsequently form a giant metallaring, [Cu{SC(O)O i Pr}]96 (2). We also demonstrate a luminescent precursor to cluster (2) can be achieved through a solventless and rapid mechanochemical synthesis. Cluster (2) is the highest nuclearity copper(I) wheel and the largest metal cluster containing a heterodichalcogen (O, S) ligand reported to date. Cluster (2) also exhibits solid-state luminescence with relatively long emission lifetimes at 4.1, 13.9 (μs). The synthetic strategy described here opens new research avenues by replacing solvent molecules in stable {Cu16} clusters with designed building units that can form new hybrid and multifunctional finite supramolecular materials. This finding may lead to the development of novel high-nuclearity materials self-assembled in a facile manner with tunable optical properties.

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Synthesis and characterization of CuI/AuI complexes derived from monothiocarbonate and tertiary phosphine ligands

Cited by 5 publications

References 88 publications

Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

Versatile Emissive Three‐Coordinated Gold(I) Systems‐Properties and Perspectives

[Cu{SC(O)OⁱPr}]₉₆: A Giant Self-Assembled Copper(I) Supramolecular Wheel Exhibiting Photoluminescence Tuning and Correlations with Dynamic Solvation and Solventless Synthesis

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Synthesis and characterization of CuI/AuI complexes derived from monothiocarbonate and tertiary phosphine ligands

Cited by 5 publications

References 88 publications

Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

Versatile Emissive Three‐Coordinated Gold(I) Systems‐Properties and Perspectives

[Cu{SC(O)OiPr}]96: A Giant Self-Assembled Copper(I) Supramolecular Wheel Exhibiting Photoluminescence Tuning and Correlations with Dynamic Solvation and Solventless Synthesis

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[Cu{SC(O)OⁱPr}]₉₆: A Giant Self-Assembled Copper(I) Supramolecular Wheel Exhibiting Photoluminescence Tuning and Correlations with Dynamic Solvation and Solventless Synthesis