Design of Supramolecular Cluster Compounds of Copper Subgroup Metals Based on Polydentate Phosphine Ligands

Grachova, Elena V.

doi:10.1134/s1070363219060045

Cited by 8 publications

(4 citation statements)

References 45 publications

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“…The latter is related to intraligand or metal-to-ligand charge transfer to the p*(CC) orbitals upon photoexcitation,f rom which radiative relaxation can also occur. [8] Concerning photoluminescence (PL) amongc oinage metal complexes, the phenomenon of metallophilicity often plays as ignificant role as well. Metallophilicity describes the tendency of metal cations to form very short metal-metal contacts, which occur mostly in the solid state.…”

Section: Introductionmentioning

confidence: 99%

Efficient Blue Phosphorescence in Gold(I)‐Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes

Feuerstein

Seifert

Jung

et al. 2020

Chemistry A European J

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The synthesis of linear symmetric ethynyl‐ and acetylide‐amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me3SiC≡CC(NDipp)2}2M2] (Dipp=2,6‐diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n‐butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh3)AuC≡CC(NDipp)2}2M2] (M=Cu, Au). The corresponding Ag complex [{(PPh3)AuC≡CC(NDipp)2}2Ag2] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue‐green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20–295 K. Emission quantum yields of up to 41 % at room temperature were determined. Furthermore, similar emissions with quantum yields of 15 % were observed for the two most brightly luminescent complexes in thf solution.

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Section: Introductionmentioning

confidence: 99%

Efficient Blue Phosphorescence in Gold(I)‐Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes

Feuerstein

Seifert

Jung

et al. 2020

Chemistry A European J

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“…[52] The alkynyl moiety is of great interest as it is often involved in photophysical processes of organometallic compounds by the metal to ligand charge transfer to the π*(C�C) orbitals and radiative relaxation could also occur after the photoexcitation. [53][54] Later in 2021, PNNP based ligand N,N'-bis[(2diphenylphosphino)phenyl]À formamidinate (dpfam À ) has been used for the site specific coordination of N and P centres to Cu I and Au I , respectively, and all of them were observed to be luminescent. [55][56][57] Herein, we report a phosphine substituted acetylide amidinate ligand containing an alkynyl moiety and a phosphine centre.…”

Section: Introductionmentioning

confidence: 99%

“…Here, the synthetic potential of alkynyl groups for the formation of multimetallic structures was investigated [52] . The alkynyl moiety is of great interest as it is often involved in photophysical processes of organometallic compounds by the metal to ligand charge transfer to the π*(C≡C) orbitals and radiative relaxation could also occur after the photoexcitation [53–54] . Later in 2021, PNNP based ligand N,N ′‐bis[(2‐diphenylphosphino)phenyl]−formamidinate (dpfam − ) has been used for the site specific coordination of N and P centres to Cu I and Au I , respectively, and all of them were observed to be luminescent [55–57] …”

Section: Introductionmentioning

confidence: 99%

Luminescent Tetranuclear Copper(I) and Gold(I) Heterobimetallic Complexes: A Phosphine Acetylide Amidinate Orthogonal Ligand Framework for Selective Complexation

Shubham,

Naina,

Roesky

2024

Chemistry A European J

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The synthesis of phosphine acetylide amidinate stabilized copper(I) and gold(I) heterobimetallic complexes was achieved by reacting ligand [{Ph2PC≡CC(NDipp)2}Li(thf)3] (Dipp = N,N’‐diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph2PC≡CC(NDipp)2}2Cu2] and the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2]. {Ph2PC≡CC(NDipp)2}2Cu2] features a Cu2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic CuI/AuI complexes [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X = Cl, C6F5). In these reactions the central ring structure is retained. In contrast, when the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2] was reacted with CuX (X = Cl, Br, I and Mes), the reaction led to rearrangement of the central ring structure to give [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X = Cl, Br, I and Mes), which feature the same the eight membered Cu2 ring as above. These compounds were also synthesized by a one‐pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties.

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“…Dinuclear or trinuclear coinage metal complexes with bridging bis-or trisphosphine ligands represent a unique class of molecules occupying a position between mononuclear complexes and nanoparticles. They have remarkable chemical and physicochemical properties due to the presence of metal-metal bonds of various energy [6]. For example, di-and tetranuclear silver nitrates with bis(diphenylphosphino)methane are known since 1983 [7].…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Silver(I) Nitrate Complexes with Bridging Bisphosphinomethanes: Argentophilicity and Luminescence

et al. 2020

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Two silver nitrate complexes with bisphosphines were obtained and characterized: [Ag(dcypm)]2(NO3)2 (1; dcypm = bis(dicyclohexylphosphino)methane) and [Ag(dppm)]2(Me2PzH)n(NO3)2 (n = 1, 2a; n = 2, 2b; dppm = bis(diphenylphosphino)methane, Me2PzH = 3,5-dimethylpyrazole). The steric repulsions of bulky cyclohexyl substituents prevent additional ligand coordination to the silver atoms in 1. Compounds obtained feature the bimetallic eight-member cyclic core [AgPCP]2. The intramolecular argenthophilic interaction (d(Ag···Ag) = 2.981 Å) was observed in complex 1. In contrast, the coordination of pyrazole led to the elongation of Ag···Ag distance to 3.218(1) Å in 2a and 3.520 Å in 2b. Complexes 1 and 2a possess phosphorescence both in the solution and solid state. Time-dependent density-functional theory (TD-DFT) calculations demonstrate the origin of their different emission profile. In the case of 1, upon excitation, the electron leaves the Ag–P bonding orbital and locates on the intramolecular Ag···Ag bond (metal-centered character). Complex 2a at room temperature exhibits a phosphorescence originating from the 3(M + LP+N)LPhCT state. At 77 K, the photoluminescence spectrum of complex 2a shows two bands of two different characters: 3(M + LP+N)LPhCT and 3LCPh transitions. The contribution of Ag atoms to the excited state in both complexes 2a and 2b decreased relative to 1 in agreement with the structural changes caused by pyrazole coordination.

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Design of Supramolecular Cluster Compounds of Copper Subgroup Metals Based on Polydentate Phosphine Ligands

Cited by 8 publications

References 45 publications

Efficient Blue Phosphorescence in Gold(I)‐Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes

Efficient Blue Phosphorescence in Gold(I)‐Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes

Luminescent Tetranuclear Copper(I) and Gold(I) Heterobimetallic Complexes: A Phosphine Acetylide Amidinate Orthogonal Ligand Framework for Selective Complexation

Dinuclear Silver(I) Nitrate Complexes with Bridging Bisphosphinomethanes: Argentophilicity and Luminescence

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