Structural and photophysical characterization of gold(I) complexes bearing naphthyl chromophores

Hobbollahi, Elnaz; List, Manuela; Redhammer, Günther J.; Zabel, Manfred; Monkowius, Uwe

doi:10.1016/j.inoche.2016.01.009

Cited by 16 publications

(40 citation statements)

References 23 publications

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“…Lifetime measurements at 78 K of K 3 [Me 4 N] 2 [Au(CN) 2 ] 5 indicate the low energy emission band is phosphorescent in nature while the high energy band is fluorescence. This dual emission behavior, as illustrated in Figure , has been previously reported in other Au(I) based coordination polymers and networks , . While the 298 K emission appears to be dominated by fluorescence emission or mixed fluorescence/phosphorescence emission, cooling of the crystal clearly causes a shift where emission by phosphorescence becomes the dominant pathway.…”

Section: Resultssupporting

confidence: 81%

Photophysical Investigation of Silver/Gold Dicyanometallates and Tetramethylammonium Networks: An Experimental and Theoretical Investigation

et al. 2019

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We report on the structural and luminescence properties of a series of d10 dicyanometallate compounds of formula K3(Me4N)2[M(CN)2]5 (M = Au and Ag). These double salts form isostructural 3D networks in which metallophilic bonding is observed between [M(CN)2]– subunits. Despite their similar structural features, stark differences in luminescence behavior between these crystals are observed. At room temperature Au‐containing crystals are bright emitters at 405 nm while the Ag analog is a weak emitter at 470 nm. At low temperatures the emission of both complexes becomes intense under UV light at a wavelength of 416 nm. Using lifetime measurements, X‐ray crystallography, and Density Functional Theory (DFT) calculations we have been able to assign these emission bands as a transition from a metal‐metal to ligand charge transfer.

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Section: Resultssupporting

confidence: 81%

Photophysical Investigation of Silver/Gold Dicyanometallates and Tetramethylammonium Networks: An Experimental and Theoretical Investigation

et al. 2019

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“…Such dual emissive behavior due to inefficient SOC from the gold atom has also been found for gold(I) and gold(III) complexes bearing derivatives of phenanthroline and naphthyl as ligands. [93][94][95] However, the linear coordination environment of the Au atom with the missing pyridine coordination in 5 and 6 leads to two effects compared to the Cu I compounds 3 and 4: 1) high energy shift of the phosphorescence and 2) decreased SOC leading to significant additional fluorescence for 5 and very weak phosphorescence for 6. The first phenomenon is most likely a result of decreased ligand conjugation in the emissive excited state of the gold compounds compared to the copper tfppy complexes, while the second finding originates from a decreased M(d) orbital overlap with the (py) orbitals (see DFT studies below).…”

Section: Resultsmentioning

confidence: 99%

C–H Activation of Fluoroarenes: Synthesis, Structure, and Luminescence Properties of Copper(I) and Gold(I) Complexes Bearing 2-Phenylpyridine Ligands

et al. 2016

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Although 2-phenylpyridine (ppy)-type have been employed very successfully for the design of luminescent Ir III and Pt II complexes, corresponding d 10-coinage metal complexes are unknown. We report on the synthesis of the first, at room temperature stable, Cu I 2-phenylpyridine (ppy)-type complexes, by C-H activation of 2-(2,3,4,5tetrafluorophenyl)pyridine (Htfppy, 1) using [Cu(OH)(IDipp)] (2) (IDipp = bis(2,6-di-isopropylphenyl)imidazole-2ylidene), or by lithiation of 1 and subsequent reaction with CuBr•SMe 2 in the presence of POP ligand (POP = bis{2-(diphenylphosphanyl)phenyl}ether) in THF, giving [Cu(tfppy)(IDipp)] (3) or [Cu(tfppy)(POP)] (4). The complexes thus obtained adopt distorted trigonal and tetrahedral coordination geometries, respectively. Gold(I) tfppy complexes with IDipp (5) or PTol 3 (6) ligands have also been prepared, showing a preference for linear coordination environments due to the non-coordinating pyridine moiety of the tfppy ligand. These structural differences have a profound effect on the photophysical properties of the coinage metal ppy compounds. The Cu I tfppy complexes exhibit intense orange-red luminescence ( max = 610 (3), 607 (4) nm) from a 3 (intra-ligand)CT state in the solid state at room temperature, with phosphorescence lifetimes of  = 8.6 (3) and 9.5 (4) s. In contrast, the linear coordination leads to weak emission of the Au I complexes, with 5 displaying simultaneous fluorescence and phosphorescence. Surprisingly, reaction of 2 with Htfppy (1) in MeCN leads to solvent activation and to isolation of a copper acetamide complex [Cu(N(H)C(O)Me)(IDipp)] (14). Scheme 1. Known Cu I Diimine and Aryl, and Unknown Copper(I) 2-Phenylpyridine Complexes. Scheme 2. Synthesis of [Cu(tfppy)(Dipp)] (3) by reaction of 1 with [Cu(tfppy)(Dipp)] (2) in the presence of molecular sieves. Scheme 3. Synthesis of tetrahedral Cu(I) and linear Au(I) tfppy complexes 4-6 by lithiation of 1.

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“…In the IR spectrum, the characteristic stretching band of the -NuC bond of the free ligand is found at 2221 cm −1 . 40 The corresponding bands for the Au(I) isonitriles are found between 2206 and 2209 cm −1 .…”

Section: Synthesismentioning

confidence: 98%

“…Therefore, 2-naphthylisonitrile (NapNC) was chosen. (NapNC)AuCl has been reported recently, 40,41 and the bromide ((NapNC)AuBr) and iodide ((NapNC)AuI) congeners have been synthesized in this study for the first time. The iodide complex is relatively unstable and forms a purple precipitate after some days in solution in the dark.…”

Section: Synthesismentioning

confidence: 99%

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Aggregation of Au(i)-complexes on amorphous substrates governed by aurophilicity

et al. 2019

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Structural and photophysical characterization of gold(I) complexes bearing naphthyl chromophores

Cited by 16 publications

References 23 publications

Photophysical Investigation of Silver/Gold Dicyanometallates and Tetramethylammonium Networks: An Experimental and Theoretical Investigation

Photophysical Investigation of Silver/Gold Dicyanometallates and Tetramethylammonium Networks: An Experimental and Theoretical Investigation

C–H Activation of Fluoroarenes: Synthesis, Structure, and Luminescence Properties of Copper(I) and Gold(I) Complexes Bearing 2-Phenylpyridine Ligands

Aggregation of Au(i)-complexes on amorphous substrates governed by aurophilicity

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