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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.

Polyethylene terephthalate (PET) is the most abundant polyester plastic, widely used in textiles and packaging, but, unfortunately, it is also one of the most discarded plastics after one use. In the last years, the enzymatic biodegradation of PET has sparked great interest owing to the discovery and subsequent mutation of PETase-like enzymes, able to depolymerize PET. FAST-PETase is one of the best enzymes hitherto proposed to efficiently degrade PET, although the origin of its efficiency is not completely clear. To understand the molecular origin of its enhanced catalytic activity, we have carried out a thorough computational study of PET degradation by the FAST-PETase action by employing classical and hybrid (QM/MM) molecular dynamics (MD) simulations. Our findings show that the rate-limiting reaction step for FAST-PETase corresponds to the acylation stage with an estimated free energy barrier of 12.1 kcal mol–1, which is significantly smaller than that calculated for PETase (16.5 kcal mol–1) and, therefore, supports the enhanced catalytic activity of FAST-PETase. The origin of this enhancement is mainly attributed to the N233K mutation, which, although sited relatively far from the active site, induces a chain folding where the Asp206 of the catalytic triad is located, impeding that this residue sets effective H-bonds with its neighboring residues. This effect makes Asp206 hold a more basic character compared to the wild-type PETase and boosts the interaction with the protonated His237 of the catalytic triad in the transition state of acylation, with the consequent decrease of the catalytic barrier and acceleration of the PET degradation reaction.

Silver chalcohalide antiperovskites represent a rather unexplored alternative to lead halide perovskites and other semiconductors based on toxic heavy metals. All synthetic approaches reported so far for Ag3SI and Ag3SBr require long synthesis times (typically days, weeks, or even months) and high temperatures. Herein, we report the synthesis of these materials using a fast and low-temperature method involving mechanochemistry. Structural and optical properties are examined experimentally and supported by first-principles calculations. Furthermore, we deposit Ag3SI as thin films by pulsed laser deposition and characterize its optoelectronic properties using optical-pump-terahertz-probe measurements, revealing a high charge-carrier mobility of 49 cm2V–1s–1. This work paves the way to the implementation of chalcohalide antiperovskites in various optoelectronic applications.

The incorporation of electroactive organic building blocks into coordination polymers (CPs) and metal–organic frameworks (MOFs) offers a promising approach for adding electronic functionalities such as redox activity, electrical conductivity, and luminescence to these materials. The incorporation of perylene moieties into CPs is, in particular, of great interest due to its potential to introduce both luminescence and redox properties. Herein, we present an innovative synthesis method for producing a family of highly crystalline and stable coordination polymers based on perylene-3,4,9,10-tetracarboxylate (PTC) and various transition metals (TMs = Co, Ni, and Zn) with an isostructural framework. The crystal structure of the PTC-TMCPs, obtained through powder X-ray diffraction and Rietveld refinement, provides valuable insights into the composition and organization of the building blocks within the CP. The perylene moieties are arranged in a herringbone pattern, with short distances between adjacent ligands, which contributes to the dense and highly organized framework of the material. The photophysical properties of PTC-Znwere thoroughly studied, revealing the presence of J-aggregation-based and monomer-like emission bands. These bands were experimentally identified, and their behavior was further understood through the use of quantum-chemical calculations. Solid-state cyclic voltammetry experiments on PTC-TMsshowed that the perylene redox properties are maintained within the CP framework. This study presents a simple and effective approach for synthesizing highly stable and crystalline perylene-based CPs with tunable optical and electrochemical properties in the solid state.

We have created a dataset of 269 perovskite solar cells, containing information about their perovskite family, cell architecture, and multiple hole-transporting materials features, including fingerprints, additives, and structural and electronic features. We propose a predictive machine learning model that is trained on these data and can be used to screen possible candidate hole-transporting materials. Our approach allows us to predict the performance of perovskite solar cells with reasonable accuracy and is able to successfully identify most of the top-performing and lowest-performing hole-transporting materials in the dataset. We discuss the effect of data biases on the distribution of perovskite families/architectures on the model’s accuracy and offer an analysis with a subset of the data to accurately study the effect of the hole-transporting material on the solar cell performance. Finally, we discuss some chemical fragments, like arylamine and aryloxy groups, which present a relatively large positive correlation with the efficiency of the cell, whereas other groups, like thiophene groups, display a negative correlation with power conversion efficiency (PCE).

Lead-free halide double perovskites (DPs) are highly tunable materials in terms of chemical composition and optical properties. One of the most widely reported DPs is Cs2AgBiBr6, which is envisaged as a promising absorber for photovoltaics. Nevertheless, its bandgap (around 1.9–2.3 eV) remains too large for common tandem solar cells. In this work, we report the mechanochemical synthesis of Sn-, Ge-, and Zn-substituted Cs2AgBiBr6in powder form; their bandgaps reach 1.55, 1.80, and 2.02 eV, respectively. These differences are rationalized through density functional theory calculations, demonstrating combined electronic and structural (disorder) effects introduced by the divalent metal-cation substituents. Finally, we present the first vacuum-deposited thin films of the Sn-substituted DP, which also show a notable narrowing of the bandgap, and this paves the way toward its implementation in photovoltaic solar cells.

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 2being derived from complex 1through 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 1in dichloromethane and 0.71 for complex 2in 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 2to 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 T1state and that their phosphorescence lifetimes are in the same order of magnitude. In contrast, the emission of complex 1can be originated only from the metal-to-ligand charge-transfer state, being the only emissive T1minimum. 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 1and 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)-2and (R)-2experience 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)-2and (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.

Molecular organization plays an essential role in organic semiconductors since it determines the extent of intermolecular interactions that govern the charge transport present in all electronic applications. The benefits of hydrogen bond-directed self-assembly on charge transport properties are demonstrated by comparing two analogous pyrrole-based, fused heptacyclic molecules. The rationally designed synthesis of these materials allows for inducing or preventing hydrogen bonding. Strategically located hydrogen bond donor and acceptor sites control the solid-state arrangement, favoring the supramolecular expansion of the π-conjugated surface and the subsequent π-stacking as proved by X-ray diffraction and computational calculations. The consistency observed for the performance of organic field-effect transistors and the morphology of the organic thin films corroborate that higher stability and thermal robustness are achieved in the hydrogen-bonded material.

Columnar polymers and liquid crystals obtained from π-conjugated cone-shaped molecules are receiving increasing interest due to the possibility of obtaining unconventional polar organizations that show anisotropic charge transport and unique chiroptical properties. However, and in contrast to the more common planar discotics, the self-assembly of conic or pyramidic molecules in solution remains largely unexplored. Here, we show how a molecular geometry change, from flat to conic, can generate supramolecular landscapes where different self-assembled species, each of them being under thermodynamic equilibrium with the monomer, exist exclusively within distinct regimes. In particular, depending on the solvent nature–aromatic or aliphatic–cone-shaped C3-symmetric subphthalocyanine 1can undergo self-assembly either as a tail-to-tail dimer, showing monomer–dimer sigmoidal transitions, or as a head-to-tail noncentrosymmetric columnar polymer, exhibiting a nucleation-elongation polymerization mechanism. Moreover, the experimental and theoretical comparison between racemic and enantiopure samples revealed that the two enantiomers (1Mand 1P) tend to narcissistically self-sort in the dimer regime, each enantiomer showing a strong preference to associate with itself, but socially self-sort in the polymer regime, favoring an alternate stacking order along the columns.

A series of molecular precursors, containing one (1and 3) or three (2and 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 1–4when 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 (FAPbI3)0.85(MAPbBr3)0.15perovskite-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.

If we aim to develop efficient synthetic models of protein receptors and enzymes, we must understand the relationships of intra- and intermolecular interactions between hosts and guests and how they mutually influence their conformational energy landscape so as to adapt to each other to maximize binding energies and enhance substrate selectivities. Here, we introduce a novel design of cofacial (ZnII)bisporphyrin cages based on dynamic imine bonding, which is synthetically simple, but at the same time highly robust and versatile, affording receptors composed of only sp2-hybridized C and N atoms. The high structural rigidity of these cages renders them ideal hosts for ditopic molecules that can fit into the cavity and bind to both metal centers, leading to association constants as high as 109M–1in chloroform. These strong binding affinities are a consequence of the remarkable chelate cooperativities attained, with effective molarity (EM) values reaching record values over 103M. However, we discovered that the cages can still adapt their structure to a more compactversion, able to host slightly smaller guests. Such a conformational transition has an energy cost, which can be very different depending on the direction of the imine linkages in the cage skeleton and which results in EMvalues 2–3 orders of magnitude lower. This interplay between cooperativity and conformational adaptability leads to strong and unusual selectivities. Not only these metalloporphyrin receptors can choose to bind preferably to a particular guest, as a function of its size, but also the guest can select which host to bind, as a function now of the host’s conformational rigidity. Such highly cooperative and selective associations are lost, however, in related flexible receptors where the imine bonds are reduced.

Fused oligothiophene-based π-conjugated organic derivatives have been widely used in electronic devices. In particular, two-dimensional (2D) heteroarenes offer the possibility of broadening the scope by extending the π-conjugated framework, which endows enhanced charge transport properties due to the potential intermolecular π–π stacking. Here, the synthesis and characterization of two new small-molecule hole-transporting materials (HTMs) for perovskite solar cells (PSCs) are reported. The newly custom-made compounds are based on dibenzoquinquethiophene (DBQT) and dibenzosexithiophene (DBST) cores, which are covalently linked to triphenylamine moieties to successfully afford the four-armed tetrakistriphenylamine (TTPA) derivatives TTPA–DBQTand TTPA–DBST. The combination of these novel central scaffolds with the electron-donor TTPA units bestow the resulting HTMs with the appropriate energy levels and, therefore, good electronic contact with the perovskite for extracting the hole efficiently. TTPA–DBQTsurpasses TTPA–DBSTnot only in terms of conductivity but also in light-to-energy conversion efficiency using conventional mesoscopic n–i–p perovskite devices, 18.1% and 14.3%, respectively. These results were systematically compared with the benchmark HTM, 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (spiro-OMeTAD). Additionally, scanning electron microscopy (SEM) hints that TTPA–DBQTforms high quality and fully homogeneous films, whereas TTPA–DBSTleads to the formation of thinner films with pinholes, which explains its lower fill factor despite its better hole-extraction properties owing to its more planar π-extended scaffold.

Synergistic experimental and theoretical studies have allowed the disentangling of the possible pathways for the supramolecular polymerization of a series of dicyanovinyl-bridged N-heterotriangulene (NHT) derivatives bearing benzamide units with achiral (1a) and chiral (1b,c) side chains. The synthesis of these bowl-shaped, self-assembling units yields a mixture of monomeric species with C3- and C1-symmetry. Both monomeric species are able to self-assemble into different supramolecular aggregates with sufficient stability to coexist in freshly prepared solutions. The dissimilar ratio of the aggregates initially generated results in different spectroscopic features and, more specifically, in the apparition of nonmirror circular dichroism (CD) spectra for chiral 1band 1c. The interconversion at room temperature of the aggregates formed by the C3- and C1-symmetry monomeric species is energetically unfavorable due to the steric hindrance between the neighboring dicyanovinyl groups within the aggregate. Heating the aggregates constituted by both monomeric species favors their disassembly and, at the same time, the conversion of the monomeric species with C1-symmetry into that with C3-symmetry by a flipping motion of one dicyanovinyl group. Cooling down the solutions back to room temperature leads to the formation of helical-like columnar aggregates based on C3-symmetry monomers showing specular CD spectra for chiral 1band 1c. The flipping motion at the molecular level described here for the bowl-shaped dicyanovinyl-bridged NHTs 1a–cis, to the best of our knowledge, the only example in which a geometric change in the monomeric species, with no participation of intramolecular noncovalent interactions, is responsible for biasing the pathway complexity that yields two different stable supramolecular architectures from a single self-assembling unit.

A complete series of experimental and theoretical investigations on the supramolecular polymerization of chiral (1and 2) and achiral (3) oligo(phenylene ethynylene) tricarboxamides (OPE-TAs) is reported. The performance of seargents-and-soldiers (SaS) and majority rules (MR) experiments has allowed deriving a full set of thermodynamic parameters, including the helix reversal penalty (HRP) and the mismatch penalty (MMP). The results described illustrate the influence exerted by the number of stereogenic centers per monomeric unit and the temperature on the chiral amplification phenomenon. While the HRP decreases upon decreasing the number of chiral side chains, the MMP follows an opposite trend. The experimental trend observed in MR experiments contrasts with that reported for benzenetricarboxamides (BTAs), for which the chiral amplification ability increases by lowering the number of stereogenic centers or increasing the temperature. Theoretical calculations predict that the rotational angle between adjacent monomeric units in the stack (ca. 18°) gradually decreases when decreasing the number of branched chiral side chains and leads to higher MMP values, in good accord with the experimental trend. The reduction of the rotational angle gives rise to less efficient H-bonding interactions between the peripheral amide functional groups and is suggested to provoke a decrease of the HRP as experimentally observed. In BTAs, increasing the number of stereogenic centers per monomeric unit results in a negligible change of the rotation angle between adjacent units (ca. 65°), and, consequently, the steric bulk increases with the number of chiral side chains, leading to higher MMP values. The data presented herein contribute to shed light on the parameters controlling the transfer and amplification of chirality processes in supramolecular polymers, highlighting the enormous influence exerted by the size of the self-assembling unit on the final helical outcome.

• We parallelize the H-LU factorization as implemented in the sequential version of H2Lib, with problems involving low-rank blocks and real H-arithmetic. • We propose the use of an auxiliary "skeleton" array to identify task dependencies. • We leverage the new OmpSs-2 model, with explicit support for weak dependencies and early release to take advantage of fine-grained nested parallelism. We address the parallelization of the LU factorization of hierarchical matrices (H -matrices) arising from boundary element methods. Our approach exploits task-parallelism via the OmpSs programming model and runtime, which discovers the data-flow parallelism intrinsic to the operation at execution time, via the analysis of data dependencies based on the memory addresses of the tasks' operands. This is especially challenging for H -matrices, as the structures containing the data vary in dimension during the execution. We tackle this issue by decoupling the data structure from that used to detect dependencies. Furthermore, we leverage the support for weak operands and early release of dependencies, recently introduced in OmpSs-2, to accelerate the execution of parallel codes with nested task-parallelism and fine-grain tasks. As a result, we obtain a significant improvement in the parallel performance with respect to our previous work. [ABSTRACT FROM AUTHOR]

“Breathing” metal–organic frameworks (MOFs) that involve changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their range of potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multifunctional “breathing” frameworks. Herein, we report the continuous breathing behavior of a tetrathiafulvalene (TTF)-based MOF, namely MUV-2, showing a reversible swelling (up to ca. 40% of the volume cell) upon solvent adsorption. Importantly, the planarity of the TTF linkers is influenced by the breathing behavior of the MOF, directly impacting on its electrochemical properties and thus opening the way for the development of new electrochemical sensors. Quantum chemical calculations and Raman spectroscopy have been used to provide insights into the tunability of the oxidation potential.

Dense linear algebra libraries, such as BLAS and LAPACK, provide a relevant collection of numerical tools for many scientific and engineering applications. While there exist high performance implementations of the BLAS (and LAPACK) functionality for many current multi-threaded architectures, the adaption of these libraries for asymmetric multicore processors (AMPs) is still pending. In this paper we address this challenge by developing an asymmetry-aware implementation of the BLAS, based on the BLIS framework, and tailored for AMPs equipped with two types of cores: fast/power-hungry versus slow/energy-efficient. For this purpose, we integrate coarse-grain and fine-grain parallelization strategies into the library routines which, respectively, dynamically distribute the workload between the two core types and statically repartition this work among the cores of the same type. Our results on an ARM ® big.LITTLE™ processor embedded in the Exynos 5422 SoC, using the asymmetry-aware version of the BLAS and a plain migration of the legacy version of LAPACK, experimentally assess the benefits, limitations, and potential of this approach from the perspectives of both throughput and energy efficiency. [ABSTRACT FROM AUTHOR]

A series of bis-cyclometalated iridium(III) complexes of general formula [Ir(ppy)2(N∧N)][PF6] (ppy–= 2-phenylpyridinate; N∧N = 2-(1H-imidazol-2-yl)pyridine (1), 2-(2-pyridyl)benzimidazole (2), 1-methyl-2-pyridin-2-yl-1H-benzimidazole (3), 2-(4′-thiazolyl)benzimidazole (4), 1-methyl-2-(4′-thiazolyl)benzimidazole (5)) is reported, and their use as electroluminescent materials in light-emitting electrochemical cell (LEC) devices is investigated. [2][PF6] and [3][PF6] are orange emitters with intense unstructured emission around 590 nm in acetonitrile solution. [1][PF6], [4][PF6], and [5][PF6] are green weak emitters with structured emission bands peaking around 500 nm. The different photophysical properties are due to the effect that the chemical structure of the ancillary ligand has on the nature of the emitting triplet state. Whereas the benzimidazole unit stabilizes the LUMO and gives rise to a 3MLCT/3LLCT emitting triplet in [2][PF6] and [3][PF6], the presence of the thiazolyl ring produces the opposite effect in [4][PF6] and [5][PF6] and the emitting state has a predominant 3LC character. Complexes with 3MLCT/3LLCT emitting triplets give rise to LEC devices with luminance values 1 order higher than those of complexes with 3LC emitting states. Protecting the imidazole N–H bond with a methyl group, as in complexes [3][PF6] and [5][PF6], shows that the emissive properties become more stable. [3][PF6] leads to outstanding LECs with simultaneously high luminance (904 cd m–2), efficiency (9.15 cd A–1), and stability (lifetime over 2500 h).

Bond breaking has emerged as a new tool to postsynthetically modify the pore structure in metal–organic frameworks since it allows us to obtain pore environments in structures that are inaccessible by other techniques. Here, we extend the concept of clip-off chemistry to archetypical ZIF-8, taking advantage of the different stabilities of the bonds between imidazolate and Zn and Fe metal atoms in heterometallic Fe-Zn-ZIF-8. We demonstrate that Fe centers can be removed selectively without affecting the backbone of the structure that is supported by the Zn atoms. This allows us to create mesopores within the highly stable ZIF-8 structure. The strategy presented, combined with control of the amount of iron centers incorporated into the structure, permits porosity engineering of ZIF materials and opens a new avenue for designing novel hierarchical porous frameworks.