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The article focuses on the concept of supramolecular cage formation that can be extended to a phenylpyrazole-based iridium complex and its use in light-emitting electrochemical cells (LECs). It mentions the advantages of these cells over traditional organic light-emitting diodes (OLEDs), including simpler architectures. It notes the limited stability of LEC devices, which is said to primarily stem from the degradation of the ionic transition-metal complexes (iTMCs) used as the active component in the emissive layer.

Two quinonoid bis(dicyanomethylene) oligothiophenes, terthiophene and quaterthiophene analogues of TCNQ, have been investigated by spectroelectrochemical experiments and density functional theory calculations. Electrochemical data show that the molecules can be both reduced and oxidized at relatively low potentials, and that the quaterthiophene derivative forms four stable redox species, the dianion, neutral, cation radical, and dication. The neutral oligomers are characterized by a strong electronic absorption in the red or near-infrared region and can be viewed as structural and electronic analogues of aromatic oligothiophenes in the dication or bipolaron state. Upon reduction, dianions, not anion radicals, are formed which absorb in the visible region. The theoretical calculations show that the dianions have aromatic oligothiophene moieties with two anionic dicyanomethylene groups. The transition from a quinonoid to an aromatic structure is fully supported by UV-vis-near-IR and vibrational spectroscopic data. Oxidation, generating cation radicals and dications, occurs at rather low potentials similar to those reported for oligothiophenes. The electronic spectra of these cations are understood from the calculations, which suggest that the oxidized species are stabilized by the partial aromatization of the oligothiophene backbone. IR spectra of the species, especially the CN stretching frequencies, confirm the structural conclusions and allow comparison with TCNQ and the TCNQ dianion. [ABSTRACT FROM AUTHOR]

The article presents a study regarding the design, synthesis, and binding abilities of macrocyclic fullerene receptors that were based on 2-[9-(1,3-diothiol-2-ylidene)anthracen-10(9H)-ylidene]-1,3-diothiole (exTTF). It mentions that macrocyclic receptor's design maintains the features of tweezers receptors but includes an alkyl linker with terminal alkenes. Ultraviolet (UV)-vis titration were conducted to estimate the binding constants of macrocyles toward C60 and C70.

The article presents a study which examines the properties of an iridium-based ionic transition-metal complex (iTMCs) which exhibits ligands interaction in order to yield stable solid-state light-emitting electrochemical cells (LECs). The results of the two-layer LEC preparation and electrochemical analysis to examine the electroluminiscent of the complex are also provided. It concludes that interligand stacking in the complex enhances stability when used in double-layer solid state LEC.

The article focuses on the study conducted in Lausanne, Switzerland regarding the development of stable single-layer light-emitting electrochemical cell using hexafluorophosphate. The authors discuss the insensitivity to the work function of the electrodes employed in light-emitting electrochemical cells. Moreover, they talk about the analysis of the orbital energies and structural analysis.

The theoretical calculation of the temperature-dependent nonradiative decay rate constant is fundamental for predicting the usefulness of transition-metal complexes for technological applications. Such a computation implies the determination of the barriers separating the emitting triplet state from metal-centered states, which are key mediators of this type of radiationless relaxation. We here do so for the two green-emitting cyclometalated Ir(III) complexes, [Ir(ppy) 2 (pyim)] + and [Ir(diFppy) 2 (dtb-bpy)] + , of general formula [Ir(C ∧ N) 2 (N ∧ N)] + , performing DFT calculations with both B3LYP and PBE0 functionals. On the basis of the obtained results and the comparison with the experimental nonradiative decay rate constants, we conclude that B3LYP provides too low energy barriers to the metal-centered states, while the PBE0 provides reasonable values. We consequently recommend to avoid the use of the commonly employed B3LYP functional for the evaluation of such an energy barrier for cyclometalated Ir(III) complexes.

The photophysical behavior of the cyclometalating Ir(III) complexes [Ir(ppy) 2 (bpy)] + , where Hppy is 2-phenylpyridine and bpy is 2,2'-bipyridine (complex 1 ), and [Ir(diFppy) 2 (dtb-bpy)] + , where diFppy is 2-(2,4-difluorophenyl)pyridine and dtb-bpy is 4,4'-di- tert -butyl-2,2'-bipyridine (complex 2 ), has been theoretically investigated by performing density functional theory calculations. The two complexes share the same molecular skeleton, complex 2 being derived from complex 1 through the addition of fluoro and tert -butyl substituents, but present notable differences in their photophysical properties. The remarkable difference in their emission quantum yields (0.196 for complex 1 in dichloromethane and 0.71 for complex 2 in acetonitrile) has been evaluated by characterizing both radiative and nonradiative decay paths. It has emerged that the probability of decaying through the nonradiative triplet metal-centered state, normally associated with the loss of the emission quantum yield, does not appear to be the reason behind the reported substantially different emission efficiency. A more critical factor appears to be the ability of complex 2 to emit from both the usual metal-to-ligand charge-transfer state and from two additional ligand-centered states, as supported by the fact that the respective minima belong to the potential energy surface of the lowest triplet T 1 state and that their phosphorescence lifetimes are in the same order of magnitude. In contrast, the emission of complex 1 can be originated only from the metal-to-ligand charge-transfer state, being the only emissive T 1 minimum. The results constitute a significant case in which the emission from ligand-centered states is the key for determining the high emission quantum yield of a complex.

The synthesis of two series of N-annulated perylene bisimides (PBIs), compounds 1 and 2 , is reported, and their self-assembling features are thoroughly investigated by a complete set of spectroscopic measurements and theoretical calculations. The study corroborates the enormous influence that the distance between the PBI core and the peripheral groups exerts on the chiroptical properties and the supramolecular polymerization mechanism. Compounds 1 , with the peripheral groups separated from the central PBI core by two methylenes and an ester group, form J-type supramolecular polymers in a cooperative manner but exhibit negligible chiroptical properties. The lack of clear helicity, due to the staircase arrangement of the self-assembling units in the aggregate, justifies these features. In contrast, attaching the peripheral groups directly to the N-annulated PBI core drastically changes the self-assembling properties of compounds 2 , which form H-type aggregates following an isodesmic mechanism. These H-type aggregates show a strong aggregation-caused quenching (ACQ) effect that leads to nonemissive aggregates. Chiral ( S ) -2 and ( R )-2 experience an efficient transfer of asymmetry to afford P - and M-type aggregates, respectively, although no amplification of asymmetry is achieved in majority rules or "sergeants-and-soldiers" experiments. A solvent-controlled stereomutation is observed for chiral ( S )- 2 and ( R )- 2 , which form helical supramolecular polymers of different handedness depending on the solvent (methylcyclohexane or toluene). The stereomutation is accounted for by considering the two possible conformations of the terminal phenyl groups, eclipsed or staggered, which lead to linear or helical self-assemblies, respectively, with different relative stabilities depending on the solvent.

Two redox and magnetically active perchlorotriphenylmethyl ( • PTM) radical units have been connected as end-capping groups to a bis(phenylene)diyne chain through vinylene linkers. Negative and positive charged species have been generated, and the influence of the bridge on their stabilization is discussed. Partial reduction of the electron-withdrawing • PTM radicals results in a class-II mixed-valence system with the negative charge located on the terminal PTM units, proving the efficiency of the conjugated chain for the electron transport between the two terminal sites. Counterintuitively, the oxidation process does not occur along the electron-rich bridge but on the vinylene units. The • PTM radicals play a key role in the stabilization of the cationic species, promoting the generation of quinoidal ring segments.

A series of molecular precursors, containing one ( 1 and 3 ) or three ( 2 and 4 ) pyrene anchors, covalently linked to porphyrins (free base or Zn), were prepared and characterized. All of them enable their π-π stacking onto low-dimensional nanocarbons including single-walled carbon nanotubes (SWCNTs) and nanographene (NG), their individualization, and their characterization. Microscopic (TEM, AFM) and spectroscopic (steady-state UV-vis and fluorescence, spectroelectrochemistry, and transient absorption measurements) techniques were at the forefront of the characterizations and were complemented by Raman spectroscopy and theoretical calculations. Of great importance is the Raman analysis, which corroborated n-doping of the nanocarbons due to the interactions with 1 - 4 when probed in the solid state. In solution, the situation is, however, quite different. Efficient charge separation was only observed for the graphene-based system NG/ 3 .

Three hole-transporting materials (HTMs) were prepared following a straightforward synthetic route by cross-linking arylamine-based ligands with a simple thieno[3,2- b ]thiophene (TbT) core. The novel HTMs were fully characterized with standard techniques to gain insight into their optical and electrochemical properties and were incorporated in solution-processed mesoporous (FAPbI 3 ) 0.85 (MAPbBr 3 ) 0.15 perovskite-based solar cells. The similar molecular structure of the synthesized HTMs was leveraged to investigate the role that the bridging units between the conjugated TbT core and the peripheral arylamine units plays on their properties and thereby on the photovoltaic response. A remarkable power conversion efficiency exceeding 18% was achieved for one of the TbT derivatives, which was slightly higher than the value measured for the benchmark spiro-OMeTAD.

Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV-vis titration experiments in CH 2 Cl 2 at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 10 8 M -1 . Calculation of the allosteric cooperative factor α for supramolecular complexes [3·1 2 ] and [4·1 2 ] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the complementary ammonium-crown ether interaction and, second, on the π-π interactions between the porphyrin rings and the C 60 moieties. Theoretical calculations have evidenced a significant decrease of the electron density in the porphyrin dimers 3 and 4 upon complexation of the first C 60 molecule, in good agreement with the negative cooperativity found in these systems. This negative effect is partially compensated by the stabilizing C 60 -C 60 interactions that take place in the more stable syn-disposition of [4·1 2 ].

We report the process of singlet exciton fission with high-yield upon photoexcitation of a quinoidal thiophene molecule. Efficient ultrafast triplet photogeneration and its yield are determined by photoinduced triplet-triplet absorption, flash photolysis triplet lifetime measurements, as well as by femtosecond time-resolved transient absorption and fluorescence methods. These experiments show that optically excited quinoidal bithiophene molecule undergoes ultrafast formation of the triplet-like state with the lifetime ∼57 μs. CASPT2 and RAS-SF calculations have been performed to support the experimental findings. To date, high singlet fission rates have been reported for crystalline and polycrystalline materials, whereas for covalently linked dimers and small oligomers it was found to be relatively small. In this contribution, we show an unprecedented quantum yield of intramolecular singlet exciton fission of ∼180% for a quinoidal bithiophene system.

In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogeneous set of reference interaction energies was computed for the supramolecular complexes constituting the L7 and S12L data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (for the S12L set) have been crucial for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy. Overall, the NL van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly bonded supramolecular systems.

Ir(III) cationic complexes with cyclometalating tetrazolate ligands were prepared for the first time, following a two-step strategy based on (i) a silver-assisted cyclometalation reaction of a tetrazole derivative with IrCl3 affording a bis-cyclometalated solvato-complex P ([Ir(ptrz)2(CH3CN)2](+), Hptrz = 2-methyl-5-phenyl-2H-tetrazole); (ii) a substitution reaction with five neutral ancillary ligands to get [Ir(ptrz)2L](+), with L = 2,2'-bypiridine (1), 4,4'-di-tert-butyl-2,2'-bipyridine (2), 1,10-phenanthroline (3), and 2-(1-phenyl-1H-1,2,3-triazol-4-yl)pyridine (4), and [Ir(ptrz)2L2](+), with L = tert-butyl isocyanide (5). X-ray crystal structures of P, 2, and 3 were solved. Electrochemical and photophysical studies, along with density functional theory calculations, allowed a comprehensive rationalization of the electronic properties of 1-5. In acetonitrile at 298 K, complexes equipped with bipyridine or phenanthroline ancillary ligands (1-3) exhibit intense and structureless emission bands centered at around 540 nm, with metal-to-ligand and ligand-to-ligand charge transfer (MLCT/LLCT) character; their photoluminescence quantum yields (PLQYs) are in the range of 55-70%. By contrast, the luminescence band of 5 is weak, structured, and blue-shifted and is attributed to a ligand-centered (LC) triplet state of the tetrazolate cyclometalated ligand. The PLQY of 4 is extremely low (<0.1%) since its lowest level is a nonemissive triplet metal-centered ((3)MC) state. In rigid matrix at 77 K, all of the complexes exhibit intense luminescence. Ligands 1-3 are also strong emitters in solid matrices at room temperature (1% poly(methyl methacrylate) matrix and neat films), with PLQYs in the range of 27-70%. Good quality films of 2 could be obtained to make light-emitting electrochemical cells that emit bright green light and exhibit a maximum luminance of 310 cd m(-2). Tetrazolate cyclometalated ligands push the emission of Ir(III) complexes to the blue, when compared to pyrazolate or triazolate analogues. More generally, among the cationic Ir(III) complexes without fluorine substituents on the cyclometalated ligands, 1-3 exhibit the highest-energy MLCT/LLCT emission bands ever reported.