Luminescent Au<sup>I</sup>–Cu<sup>I</sup> Triphosphane Clusters That Contain Extended Linear Arylacetylenes

Shakirova, Julia R.; Grachova, Elena V.; Melekhova, Anna A.; Krupenya, Dmitrii V.; Gurzhiy, Vladislav V.; Karttunen, Antti J.; Koshevoy, Igor O.; Melnikov, Alexei S.; Tunik, Sergey P.

doi:10.1002/ejic.201200362

Cited by 21 publications

(13 citation statements)

References 71 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%

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%

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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“…Four copper atoms are incorporated inside the cage being p-coordinated to the À C C À bonds and further supported by metallophilic Au-Cu interactions to form heteronuclear {(tppm)Au 3 Cu} end-capping clusters,w hich are structurally close to the previously described [(tppm)Au 3 Cu(C 2 R) 3 ] + species. [16] Computationally optimized geometries of 1 and 2 (DFT-PBE0-D3, Figure 2) in general comply with experimental Scheme 1. Synthesis of assemblies 1, 2 and their transformation into silver congeners 1Ag, 2Ag.…”

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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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“…Styrene and vinyltoluene were distilled prior to use. 4-Bromo-p-terphenyl was prepared according to a published procedure [20]; a white powder was obtained with an 80% yield after purification. N-(2ethylhexyl carbazole) was prepared according to our previous work [21].…”

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confidence: 99%

Progress in Fast and Red Plastic Scintillators

Hamel

2022

Chemosensors

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Radiological detection where Cherenkov residual background can be prominent requires scintillators with increased emission wavelength. Cherenkov residual background precludes the use of UV-emitting sensors such as plastic scintillators. However, the literature is scarce in red-emitting plastic scintillators and only one commercial scintillator is currently available (BC-430, from Saint-Gobain Crystals and Detectors). In addition, X-ray imaging or time-of-flight positron emission tomography (ToF-PET) applications are also demanding on this type (color) of scintillators, but such applications also require that the material displays a fast response, which is not particularly the case for BC-430. We present herein our latest developments in the preparation and characterization of fast and red plastic scintillators for this application. Here, ‘fast’ means nanosecond range decay time and ‘red’ is an emission wavelength shifted towards more than 550 nm. At first, the strategy to the preparation of such material is explained by decomposing the scintillator to fundamental elements. Each stage is then optimized in terms of decay time response, then the elemental bricks are arranged to give plastic scintillator formulations that are compatible with the abovementioned characteristics. The results are compared with the red-emissive BC-430 commercial plastic, and the ultra-fast, violet-emitting BC-422Q 1% plastic. In particular, the first-time use of trans-4-dimethylamino-4′-nitrostilbene in the scintillation field as a red wavelength shifter allowed preparing plastic scintillators with the following properties: λemmax 554 nm, photoluminescence decay time 4.2 ns, and light output ≈ 6100 ph/MeV. This means a scintillator almost as bright as BC-430 but at least three times faster. This new sensor might provide useful properties for nuclear instrumentation.

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Luminescent Au^I–Cu^I Triphosphane Clusters That Contain Extended Linear Arylacetylenes

Cited by 21 publications

References 71 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

Progress in Fast and Red Plastic Scintillators

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Luminescent AuI–CuI Triphosphane Clusters That Contain Extended Linear Arylacetylenes

Cited by 21 publications

References 71 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

Progress in Fast and Red Plastic Scintillators

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Luminescent Au^I–Cu^I Triphosphane Clusters That Contain Extended Linear Arylacetylenes