Five cationic iridium(III) complexes ( 1 – 5 ) were synthesized exploiting two triazole-based cyclometalating ligands, namely, 1-methyl-4-phenyl-1 H -1,2,3-triazole ( A ) and the corresponding mesoionic carbene 1,3-dimethyl-4-phenyl-1 H -1,2,3-triazol-5-ylidene ( B ). From the combination of these two ligands and the ancillary one, i.e., 4,4′-di- tert -butyl-2,2′-bipyridine (for 1 – 3 ) or tert -butyl isocyanide (for 4 and 5 ), not only the typical bis-heteroleptic complexes but also the much less explored tris-heteroleptic analogues ( 2 and 5 ) could be synthesized. The redox and emission properties of all of the complexes are effectively fine-tuned by the different ligands: (i) cyclometalating ligand A induces a stronger highest occupied molecular orbital (HOMO) stabilization compared to B and leads to complexes with progressively narrower HOMO–lowest unoccupied molecular orbital (LUMO) and redox gaps, and lower emission energy; (ii) complexes 1 – 3 , equipped with the bipyridine ancillary ligand, display fully reversible redox processes and emit from predominantly metal-to-ligand charge transfer (MLCT) states with high emission quantum yields, up to 60% in polymeric matrix; (iii) complexes 4 and 5 , equipped with high-field isocyanide ligands, display irreversible redox processes and high-energy emission from strongly ligand-centered triplets with long emission lifetimes but relatively low quantum yields (below 6%, both in room-temperature solution and in solid state). This work demonstrates the versatility of phenyl-triazole derivatives as cyclometalating ligands with different chelation modes (i.e., C ∧ N and C ∧ C:) for the synthesis of photoactive iridium(III) complexes with highly tunable properties.
This paper presents the observation of four-top-quark ($$t\bar{t}t\bar{t}$$ t t ¯ t t ¯ ) production in proton-proton collisions at the LHC. The analysis is performed using an integrated luminosity of 140 $$\hbox {fb}^{-1}$$ fb - 1 at a centre-of-mass energy of 13 TeV collected using the ATLAS detector. Events containing two leptons with the same electric charge or at least three leptons (electrons or muons) are selected. Event kinematics are used to separate signal from background through a multivariate discriminant, and dedicated control regions are used to constrain the dominant backgrounds. The observed (expected) significance of the measured $$t\bar{t}t\bar{t}$$ t t ¯ t t ¯ signal with respect to the standard model (SM) background-only hypothesis is 6.1 (4.3) standard deviations. The $$t\bar{t}t\bar{t}$$ t t ¯ t t ¯ production cross section is measured to be $$22.5^{+6.6}_{-5.5}$$ 22 . 5 - 5.5 + 6.6 fb, consistent with the SM prediction of $$12.0 \pm 2.4$$ 12.0 ± 2.4 fb within 1.8 standard deviations. Data are also used to set limits on the three-top-quark production cross section, being an irreducible background not measured previously, and to constrain the top-Higgs Yukawa coupling and effective field theory operator coefficients that affect $$t\bar{t}t\bar{t}$$ t t ¯ t t ¯ production.
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