Luminescence behaviour of Au(<scp>i</scp>)–Cu(<scp>i</scp>) heterobimetallic coordination polymers based on alkynyl-tris(2-pyridyl)phosphine Au(<scp>i</scp>) complexes

Petrovskii, S. K.; Paderina, Aleksandra; Sizova, Anastasia A.; Baranov, Andrey Yu.; Artem’ev, Alexander V.; Sizov, V. V.; Grachova, Elena V.

doi:10.1039/d0dt02583f

Cited by 17 publications

(16 citation statements)

References 44 publications

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“…Here, a wide range of luminescent gold(I) complexes have been synthesized and their photophysical parameters have been thoroughly studied. − They include planar three-coordinate complexes. In this regard, the photoluminescence properties of three-coordinate complexes 1 – 5 were studied.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Shmelev

Okubazghi

Abramov

et al. 2022

Crystal Growth & Design

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A series of new cationic complexes [(PPh3)Au(L)](OTf) (L = 1,10-phenanthroline (phen) (1); 5,6-dimethyl-1,10-phenanthroline (dmphen) (2); 5,6-epoxy-5,6-dihydro-1,10-phenanthroline (ephen) (3); dimethyl 2,2’-biquinoline-4,4’-dicarboxylate (dmcbiq) (4); 2,3,4,5,6,7,8,9-octachloro-1,10-phenantroline (ocphen) (5)) were obtained in high yields by the standard ligand exchange reactions from [(PPh3)AuCl]. The compounds were characterized by analytical and spectroscopic methods. For all compounds, the crystal structure was established using X-ray diffraction analysis. In all structures, an atypical asymmetric mode of coordination of the diimine ligand (one shortened and the second elongated Au–N bond) was found, which is a consequence of the so-called antichelate effect. Structures 1–3 with electron-donating substituents (H, methyl, epoxide) are the most asymmetric, while structures 4 and 5 with electron-withdrawing groups (CO2Me and Cl) are the least asymmetric. According to the results of the density functional theory (DFT) calculations, both Au–N bonds are covalent, and the geometry around gold(I) can be considered as a distorted triangular one. Cationic complexes [(PPh3)Au(L)]+ form dimers in the crystal structure due to π–π interactions, the calculated energy of which reaches 4.2 kcal·mol–1 in the case of structure 5. These dimers in 5 additionally interact with OTf– anions through different kinds of contacts with a calculated total energy of 8.8 kcal·mol–1. Inside the {[(PPh3)Au(ocphen)]2}2+ associates, intermolecular Au···Cl noncovalent interactions were also found. Remarkably, the dimers in 5 are built through nonclassical π–π interactions between geometrically different parts of the ocphen ligand, which is a consequence of its asymmetric coordination to the gold(I) center. All complexes show multiple photoluminescence in the solid state at room temperature. The lifetimes of the excited state are in the microsecond range, which is characteristic of phosphorescence. Time-dependent DFT (TD-DFT) calculations reveal that electronic transitions of different nature are responsible for the photoluminescence of complexes 1–5.

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Section: Resultsmentioning

confidence: 99%

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Shmelev

Okubazghi

Abramov

et al. 2022

Crystal Growth & Design

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“…These compounds have been used as precursors to obtain heterometallic clusters by the coordination of Cu(I) in the chemical structure. As is known, both the N-atom in the phosphane ligand and the alkynyl moiety may coordinate with the copper(I) metal centers and provide ancillary support to bimetallic cluster formation, thanks to the additional expected coordination to the Au(I) atoms (Au(I)···Cu(I) weak contacts). ,,− The obtained heterometallic complexes have been studied as red phosphorescence emitters and singlet oxygen photosensitizers.…”

Section: Introductionmentioning

confidence: 99%

Heterometallic Au(I)–Cu(I) Clusters: Luminescence Studies and¹O₂Production

2023

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Two different organometallic gold(I) compounds containing naphthalene and phenanthrene as fluorophores and 2-pyridyldiphenylphosphane as the ancillary ligand were synthesized (compounds 1 with naphthalene and 2 with phenanthrene). They were reacted with three different copper(I) salts with different counterions (PF6 –, OTf–, and BF4 –; OTf = triflate) to obtain six Au(I)/Cu(I) heterometallic clusters (compounds 1a–c for naphthalene derivatives and 2a–c for phenanthrene derivatives). The heterometallic compounds present red pure room-temperature phosphorescence in both solution, the solid state, and air-equilibrated samples, as a difference with the dual emission recorded for the gold(I) precursors 1 and 2. The presence of Au(I)–Cu(I) metallophilic contacts has been identified using single-crystal X-ray diffraction structure resolution of two of the compounds, which play a direct role in the resulting red-shifted emission with respect to the gold(I) homometallic precursors. Polystyrene (PS) and poly(methyl methacrylate) (PMMA) polymeric matrices were doped with our luminescent compounds, and the resulting changes in their emissive properties were analyzed and compared with those previously recorded in the solution and the solid state. All complexes were tested to analyze their ability to produce 1O2 and present very good values of ΦΔ up to 50%.

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“…4−6 This type of bond occurs in all areas of gold chemistry, especially in catalysis 7 and photoluminescence. 8,9 Complexes containing P-donor ligands occupy a prominent place in gold(I) coordination chemistry, and many structurally characterized examples feature the expected Au(I)−Au(I) bonds. 10,11 It has been found that even coordination compounds with an extended ligand framework assemble in the solid state in such a way that the Au(I)−Au(I) bonds can contribute to overall stability.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Most reports of metal–metal bonding deal with the solid state, where X-ray diffraction (XRD) structural parameters provide accurate information about metal–metal distances to reveal short ones. Such short distances are often observed in gold(I) complexes, generally referred to as Au(I)–Au(I) bonding. − This type of bond occurs in all areas of gold chemistry, especially in catalysis and photoluminescence. , Complexes containing P-donor ligands occupy a prominent place in gold(I) coordination chemistry, and many structurally characterized examples feature the expected Au(I)–Au(I) bonds. , It has been found that even coordination compounds with an extended ligand framework assemble in the solid state in such a way that the Au(I)–Au(I) bonds can contribute to overall stability.…”

Section: Introductionmentioning

confidence: 99%

Au–Au Chemical Bonding in Nitronyl Nitroxide Gold(I) Derivatives

et al. 2022

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Gold(I) derivatives of nitronyl nitroxide (NN) stabilized by complexation with phosphine ligands were designed to promote dimerization of the paramagnets in the solid state via Au–Au bonding. The complexes were successfully synthesized by the reaction of the corresponding phosphine [n-Bu3P or (4-FC6H4)3P], AuCl(THT), and NN–H under basic conditions in high yields. The gold(I) complexes were characterized by cyclic voltammetry, electron spin resonance, infrared, and UV/vis spectroscopy supported by quantum chemical calculations. Crystallographic analyses of the complexes showed that they possess Au–Au bonds (2.930 and 3.095 Å). The Au–Au bonding was confirmed by density functional theory calculations and quantum theory of “atoms in molecules” and natural bond orbital analyses, which made it possible to determine bond critical points (3, −1) and Au–Au bond orders (0.36 and 0.23) as well as to estimate the orbital contribution to the energy of Au–Au bonds (12.0 and 8.6 kcal/mol).

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Luminescence behaviour of Au(i)–Cu(i) heterobimetallic coordination polymers based on alkynyl-tris(2-pyridyl)phosphine Au(i) complexes

Abstract: A set of alkynyl-tris(2-pyridyl)phosphine Au(I) complexes was synthesized and characterized. Free coordination functions on the ligand environment periphery, namely ‘scorpionate’ PPy3 and C≡C bond, allowed these ditopic metalloligands to be...

Cited by 17 publications

References 44 publications

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Heterometallic Au(I)–Cu(I) Clusters: Luminescence Studies and¹O₂Production

Au–Au Chemical Bonding in Nitronyl Nitroxide Gold(I) Derivatives

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Luminescence behaviour of Au(i)–Cu(i) heterobimetallic coordination polymers based on alkynyl-tris(2-pyridyl)phosphine Au(i) complexes

Abstract: A set of alkynyl-tris(2-pyridyl)phosphine Au(I) complexes was synthesized and characterized. Free coordination functions on the ligand environment periphery, namely ‘scorpionate’ PPy3 and C≡C bond, allowed these ditopic metalloligands to be...

Cited by 17 publications

References 44 publications

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Heterometallic Au(I)–Cu(I) Clusters: Luminescence Studies and1O2Production

Au–Au Chemical Bonding in Nitronyl Nitroxide Gold(I) Derivatives

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Heterometallic Au(I)–Cu(I) Clusters: Luminescence Studies and¹O₂Production