RESUMEN
Herein, we report the inaugural instance of NHSi-coordinated copper amide emitters (2-5). These complexes exhibit thermally activated delayed fluorescence (TADF) and singlet-triplet dual emission in anaerobic conditions. The NHSi-Cu-diphenylamide (2) complex demonstrates TADF with a very small ΔEST gap (0.01 eV), an absolute quantum yield of 11%, a radiative rate of 2.55×105 s-1, and a short τTADF of 0.45 µs in the solid state. The dual emissive complexes (3-5) achieve an absolute quantum yield of up to 20% in the solid state with a kISC rate of 1.82×108 s-1 and exhibit room temperature phosphorescence (RTP) with lifetimes up to 9 ms. The gradual decrease in the intensity of the triplet state of complex 3 under controlled oxygen exposure demonstrates its potential for future oxygen-sensing applications. Complexes 2 and 3 have been further utilized to fabricate converted LEDs, paving the way for future OLED production using newly synthesized NHSi-Cu-amides.
RESUMEN
Herein, we report the synthesis of a series of bis(silanechalcogenones) [Ch = Te (2), S (3), or Se (4)] using an N-heterocyclic silylene-based SiCSi pincer ligand (1). 2 is the first example of a bis(silanetellurone) derivative. The bonding patterns of 2-4 were extensively studied by natural bond orbital, quantum theory of atoms in molecules, and noncovalent interaction index analyses, and these exhibit weak C-H···Ch interaction. The analogous reaction of 1 with trimethyl N-oxide produced a novel bis(cyclosiloxane) derivative (5). All of the complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear nuclear magnetic resonance (1H, 13C, and 29Si) spectroscopy, and high-resolution mass spectrometry.
RESUMEN
We have utilised the 4,6-di-tert-butyl resorcinol bis(diphenylphosphinite) (POCOP) ligand for exploring its coordination ability towards group 11 metal centres. The treatment of the bidentate ligand 1 with various coinage metal precursors afforded a wide range of structurally diverse complexes 2-12, depending upon the metal precursors used. This furnishes several multinuclear Cu(I) complexes with dimeric (2) and tetrameric cores (3, 4, and 5). The tetrameric stairstep complex 4 shows thermochromic behaviour, whereas the dimeric complex 2 and tetrameric complex 3 show luminescence properties at cryogenic temperatures. Interestingly, the halide substitution reaction of the dimeric complex 2 with KPPh2 produces a unique mixed phosphine-based tetrameric Cu(I) complex, 5. Treatment of the POCOP ligand with [CuBF4(CH3CN)4] in the presence of 2,2'-bipyridine afforded heteroleptic complex 6, consisting of tri- and tetra-coordinated cationic Cu(I) centres. Furthermore, we could also isolate cubane (8) and stairstep (9) complexes of Ag(I). The cationic Au(I) complex (12) was obtained from the dinuclear Au(I) complex of POCOP, 11. Complex 12 revealed the presence of a strong intramolecular aurophilic interaction with an Auâ¯Au bond distance of 3.1143(9) Å. Subsequently, the photophysical properties of these complexes have been studied. All the complexes were characterised by single-crystal X-ray diffraction studies, routine NMR techniques, and mass spectroscopy.
RESUMEN
Group 11 metal (M = Cu, Ag, Au) complexes of heavier tetrylenes (namely, germylene and stannylene) have been studied for several years now. However, the field is mainly unexplored for their potential application either in homogeneous catalysis or in photophysical properties regardless of how the current reports allude to the rich and fascinating chemistry of group 14 elements. In this mini-review, we attempted to summarize the recent advances of heavier tetrylene-stabilized coinage metal complexes, which are majorly dominated by structure elucidation studies. This comprehensive summary intends to help researchers design and fine-tune the tetrylene ligand framework that can lead to coinage metal complexes for future applications as photoemitters in organic light-emitting diode fabrication and efficient catalysts in homogeneous catalysis.
RESUMEN
This article intends to highlight and comprehensively summarize the recent developments in the field of silylene-coinage metal chemistry. Recent years have witnessed exponential growth in the utilization of N-heterocyclic silylenes as ligands in transition metal chemistry. Still, silylene-coinage metal complexes have only started to appear very recently. Particular attention is focused on the synthetic approaches to silylene-coinage metal complexes and their unusual properties derived from the spectroscopic and crystallographic data. Recent studies have demonstrated that silylene-coinage metal complexes exhibit catalytic efficiency towards hydrosilylation, copper-catalyzed alkyne azide cycloaddition (CuAAC), and glycosidation reactions. Although the chemistry of silylene-coinage metal complexes has only begun to blossom, these findings justify the need for a review at this stage of development. This article will summarize the previous work on silylene-coinage metal complexes followed by recent advances and conclude with future possibilities.
RESUMEN
Herein we report the syntheses, X-ray structures and photophysical studies of the dinuclear dimeric gold(i) complexes [ClAu(C6H5N)(PPh2)2]2 (1), [Au(C6H5N)(PPh2)2]2[SbF6]2 (2) and [Au(2,6-Me2C6H3N)(PPh2)2]2[SbF6]2 (4). We have used ligands with different substituents to see the effect of the substituents on the photophysical properties. All these complexes feature strong intramolecular AuAu interactions (2.7987-3.0056 Å) and were found to exhibit excellent luminescence properties with high quantum yields as well as different colors of emission.