Self‐Assembly of Supramolecular Luminescent AuI–CuI Complexes: “Wrapping” an Au6Cu6 Cluster in a [Au3(diphosphine)3]3+ “Belt”

Koshevoy, Igor O.; Koskinen, Laura; Haukka, Matti; Tunik, Sergey P.; Serdobintsev, P. Yu.; Melnikov, Alexei S.; Pakkanen, Tapani A.

doi:10.1002/anie.200800452

Cited by 118 publications

(45 citation statements)

References 17 publications

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“…39 The extinction coefficients at the maximum of the absorption band increase with the number of chromophores present in the molecules. These are higher than those reported by analogous diphosphane derivatives, 29,41,50 showing slight deviations of the monotonic increase due to differences in the intramolecular stacking interactions, where higher broadening leads to lower extinction coefficient at the maximum of the band.…”

Section: Photophysical Characterizationcontrasting

confidence: 62%

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

et al. 2017

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A series of alkynyl gold(I) tri and tetratopic metallaligands of the type [Au 3 (CuC-R) 3 (μ 3 -triphosphane)] (R = 2,2'-bipyridin-5-yl or C 10 H 7 N 2 , 2,2':6',2''-terpyridin-4-yl or C 15 H 10 N 3 ; triphosphane = 1,1,1-tris(diphenylphosphanyl)ethane or triphos, 1,3,5-tris(diphenylphosphanyl)benzene or triphosph) and [Au 4 (CuC-R) 4 (μ 4 -tetraphosphane)] (R = C 10 H 7 N 2 , C 15 H 10 N 3 ; tetraphosphane = tetrakis(diphenylphosphanylmethyl)methane or tetraphos, 1,2,3,5-tetrakis(diphenylphosphanyl)benzene or tpbz, tetrakis(diphenylphosphaneylmethyl)-1,2-ethylenediamine or dppeda) were obtained in moderate to good yields. All complexes could be prepared by a reaction between the alkynyl gold(I) polymeric species [Au(CuC-R)] n and the appropriate polyphosphane. An alternative strategy that required the previous synthesis of the appropriate acetylacetonate precursors [Au n (acac) n (μ n -polyphosphane)] ("acac method") was assayed, nevertheless only the polyacac derivatives The photophysical properties of the synthesized compounds were carefully studied and used as a probe of their possible use as multidentate ligands for Cu(I) and Zn(II). The UV-Vis speciation studies of the complexation reactions were conducted via metal titration and, in most cases the dangling units of the ligand were found to behave in a fairy independent manner. While in the case of Cu(I) multiple equilibria exist in solution a single complex is detected for Zn(II) under the conditions studied.

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Section: Photophysical Characterizationcontrasting

confidence: 62%

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

et al. 2017

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“…3). As it is well-known that copper, silver, and gold ions preferentially coordinate to alkynes via end-on σ or side-on πbonding, 27 In the solid-state structure of compound 7 an inversion centre is located in the middle of the rhomboid spanned by Cu1-Au2-Cu1'-Au2', whose angles were found to be Cu1-Au2-Cu1' 109.21(2)° and Au2-Cu1-Au2` 70.79(2)°. Hence, the Au 2 Cu 2unit is in a perfectly planar arrangement as the interior angles sum up to 360°.…”

Section: Resultsmentioning

confidence: 99%

Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

et al. 2015

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Phenylpropynyl-functionalized imidazolium salts, as well as their gold complexes, were prepared in excellent yields affording suitable starting materials for metal cluster synthesis. The reactions of these gold complexes with coinage metal phenylacetylides [M(CCPh)](x) (M = Cu, Ag) resulted in the formation of novel heterometallic hexanuclear clusters which exhibit mixed metallophillic interactions and intense white photoluminescence at low temperature.

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“…5,9–17,19–41 A number of examples of short argentophilic contacts down to 2.637(1) Å, found in [Et 4 N] 2 [(Ag-(Sn 2 B 11 H 11 )bipy) 2 ], 41 have been reported. 19,21,42–44 In particular, heterometallic complexes 9,12,27,29,32,45–49 have recently attracted interest because of their efficient luminescence.…”

Section: Introductionmentioning

confidence: 99%

Shedding Light on the Photochemistry of Coinage-Metal Phosphorescent Materials: A Time-Resolved Laue Diffraction Study of an Ag^I–Cu^I Tetranuclear Complex

et al. 2014

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The triplet excited state of a new crystalline form of a tetranuclear coordination d10–d10-type complex, Ag2Cu2L4 (L = 2-diphenylphosphino-3-methylindole ligand), containing AgI and CuI metal centers has been explored using the Laue pump–probe technique with ≈80 ps time resolution. The relatively short lifetime of 1 μs is accompanied by significant photoinduced structural changes, as large as the Ag1···Cu2 distance shortening by 0.59(3) Å. The results show a pronounced strengthening of the argentophilic interactions and formation of new Ag···Cu bonds on excitation. Theoretical calculations indicate that the structural changes are due to a ligand-to-metal charge transfer (LMCT) strengthening the Ag···Ag interaction, mainly occurring from the methylindole ligands to the silver metal centers. QM/MM optimizations of the ground and excited states of the complex support the experimental results. Comparison with isolated molecule optimizations demonstrates the restricting effect of the crystalline matrix on photoinduced distortions. The work represents the first time-resolved Laue diffraction study of a heteronuclear coordination complex and provides new information on the nature of photoresponse of coinage metal complexes, which have been the subject of extensive studies.

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Self‐Assembly of Supramolecular Luminescent Au^I–Cu^I Complexes: “Wrapping” an Au₆Cu₆ Cluster in a [Au₃(diphosphine)₃]³⁺ “Belt”

Cited by 118 publications

References 17 publications

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

Shedding Light on the Photochemistry of Coinage-Metal Phosphorescent Materials: A Time-Resolved Laue Diffraction Study of an Ag^I–Cu^I Tetranuclear Complex

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Self‐Assembly of Supramolecular Luminescent AuI–CuI Complexes: “Wrapping” an Au6Cu6 Cluster in a [Au3(diphosphine)3]3+ “Belt”

Cited by 118 publications

References 17 publications

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

Shedding Light on the Photochemistry of Coinage-Metal Phosphorescent Materials: A Time-Resolved Laue Diffraction Study of an AgI–CuI Tetranuclear Complex

Contact Info

Product

Resources

About

Self‐Assembly of Supramolecular Luminescent Au^I–Cu^I Complexes: “Wrapping” an Au₆Cu₆ Cluster in a [Au₃(diphosphine)₃]³⁺ “Belt”

Shedding Light on the Photochemistry of Coinage-Metal Phosphorescent Materials: A Time-Resolved Laue Diffraction Study of an Ag^I–Cu^I Tetranuclear Complex