Alkynyl triphosphine copper complexes: synthesis and photophysical studies

Chakkaradhari, Gomathy; Belyaev, Andrey; Karttunen, Antti J.; Sivchik, V. V.; Tunik, Sergey P.; Koshevoy, Igor O.

doi:10.1039/c5dt01870f

Cited by 14 publications

(17 citation statements)

References 76 publications

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“…The geometry of the ligand environment is nearly linear with the N–Au–C≡C bond angles in the 176–178° range. The Au–N and Au–C≡C bond lengths are in agreement with values obtained for analogous gold(I)–alkynyl complexes , …”

Section: Resultssupporting

confidence: 85%

“…The Au-N and Au-C≡C bond lengths are in agreement with values obtained for analogous gold(I)-alkynyl complexes. [29,[33][34][35][36][37][38] The solid-state structure of 1 displays different types of short intermolecular contacts. Two molecules of the compound form "head-to-head" dimers through π-π interactions between the aromatic systems of the ppiq ligands, which are separated by a distance of 3.39 Å (Figure 2a).…”

Section: Introductionmentioning

confidence: 99%

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Gold(I)–Alkynyl Complexes with an N‐Donor Heterocyclic Ligand: Synthesis and Photophysical Properties

et al. 2017

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A series of AuI–alkynyl complexes, containing an N‐donor ligand (2‐phenylpyrido[2,1‐a]pyrrolo[3,2‐c]isoquinoline) coordinated through the pyrrole nitrogen atom, were synthesized and characterized using X‐ray crystallography and NMR spectroscopy. The obtained compounds are luminescent in solution and in the solid state, and the emission intensity depends on the nature of the alkynyl ligand to give values of quantum yield equal to 8.0 and 6.5 % for complexes 3 and 4, respectively, in dichloromethane solution at room temperature. The observed emission is ligand‐centred fluorescence that is atypical for complexes of this type, which usually display phosphorescence determined by strong spin‐orbit coupling with the heavy‐metal ion. DFT calculations of the electronic structure of the complexes showed that the contribution of the gold orbitals to the states responsible for emission is nearly negligible and results in a low intersystem crossing rate and suppression of phosphorescence in the complexes studied.

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Section: Resultssupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Gold(I)–Alkynyl Complexes with an N‐Donor Heterocyclic Ligand: Synthesis and Photophysical Properties

et al. 2017

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“…[15] Then ucleation, however, can be limited by using the appropriate multidentate ligands like tris(diphenylphosphanyl)methane (tppm), which has been applied for the preparation of as eries of tetrametallic alkynyl species [(tppm)Au 3 Cu-(C 2 R) 3 ] + . [16] Thes ynthetic protocol involves the reaction of al abile trigold complex [(tppm)Au 3 (tht) 3 ] 3+ (tht = tetrahydrothiophene) with equimolar quantities of the corresponding star-shaped trialkyne, [17] [Cu(NCMe) 4 ]X and abase (trie-thylamine,S cheme 1) to give heterometallic aggregates [(tppm)Au 3 Cu{(C 2 ) 3 R}] 4 4+ (R = 1,3,5-(4-C 6 H 4 ) 3 C 6 H 3 , 1;1 ,3,5-(4-HC 2 C 6 H 4 -4-C 2 C 6 H 4 ) 3 C 6 H 3 , 2). TheE SI + mass spectra of both compounds display the signals of quadruply charged molecular cations,F igure 1.…”

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confidence: 99%

Heterometallic Cluster‐Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

et al. 2018

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Combining the star-shaped alkynyl ligands with low-nuclearity gold-copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φ =0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.

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“…around 355 nm gives a strong emission at 447 nm, which are found in other copper(I) complexes [15][16][17][18].…”

Section: Methodsmentioning

confidence: 59%

Synthesis and properties of an unexpected trinuclear copper(I) complex supported by diphenylphosphinomethane

Tang

Lin

Zhan

et al. 2016

Inorganic Chemistry Communications

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The reaction of CuCl 2 2H 2 O, diphenylphosphinomethane (dppm), and tetracyanoethylene (TCNE) affords one unexpected trinuclear copper(I) complex, [Cu I 3 (dppm) 3 ( 3-Cl) 2 ][TCMA] 1 (TCMA: tricyanoacrylmethylate, a new compound deriving from TCNE). Structural study shows that three copper atoms are connected by dppm ligands bridging each edge to form a Cu 3 P 6 unit. At room temperature, 1 appears photoluminescence at 447 nm. And 1 also can electrocatalyze hydrogen generation from acetic acid with a turnover frequency (TOF) of 99.9 moles of H 2 per mole of catalyst per hour at an overpotential of 941.6 mV.

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Alkynyl triphosphine copper complexes: synthesis and photophysical studies

Abstract: A chelating triphosphine was used to synthesize luminescent mono-, di- and trinuclear copper(i) alkynyl complexes, the photophysical properties of which are determined by the nature of alkynyl groups.

Cited by 14 publications

References 76 publications

Gold(I)–Alkynyl Complexes with an N‐Donor Heterocyclic Ligand: Synthesis and Photophysical Properties

Gold(I)–Alkynyl Complexes with an N‐Donor Heterocyclic Ligand: Synthesis and Photophysical Properties

Heterometallic Cluster‐Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

Synthesis and properties of an unexpected trinuclear copper(I) complex supported by diphenylphosphinomethane

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