Steering perovskite precursor solutions for multijunction photovoltaics.

Multijunction photovoltaics (PVs) are gaining prominence owing to their superior capability of achieving power conversion efficiencies (PCEs) beyond the radiative limit of single-junction cells, where improving narrow bandgap tin-lead perovskites is critical for thin-film devices. With a focus on understanding the chemistry of tin-lead perovskite precursor solutions, we herein find that Sn(II) species dominate interactions with precursors and additives and uncover the exclusive role of carboxylic acid in regulating solution colloidal properties and film crystallisation, and ammonium in improving film optoelectronic properties. Materials that combine these two function groups, amino acid salts, considerably improve the semiconducting quality and homogeneity of perovskite films, surpassing the effect of the individual functional groups when introduced as part of separate molecules.

Circularly polarized luminescence induction on a Tb(III) complex with a tris(-butylaryloxide)-functionalized 1,4,7-triazacyclononane ligand coordinating chiral 1-phenylethylamine.

Circularly polarized luminescence (CPL) activity was induced on a racemic Tb complex with a 1,4,7-triazacyclononane-based tris-phenoxide ligand by the coordination of a chiral 1-phenylethylamine ligand to the Tb centre. -Butyl groups at the -position of the phenoxide moieties were found to be important for efficient CPL induction in the Tb complex.

Single-gold etching at the hypercarbon atom of C-centred hexagold(I) clusters protected by chiral N-heterocyclic carbenes.

Chemical etching of nano-sized metal clusters at the atomic level has a high potential for creating metal number-specific structures and functions that are difficult to achieve with bottom-up synthesis methods. In particular, precisely etching metal atoms one by one from nonmetallic element-centred metal clusters and elucidating the relationship between their well-defined structures, and chemical and physical properties will facilitate future materials design for metal clusters. Here we report the single-gold etching at a hypercarbon centre in gold(I) clusters.

'Passivated Precursor' Approach to All-Alkynyl-Protected Gold Nanoclusters and Total Structure Determination of Au.

A 'passivated precursor' approach is developed for the efficient synthesis and isolation of all-alkynyl-protected gold nanoclusters. Direct reduction of dpa-passivated precursor Au-dpa (Hdpa=2,2'-dipyridylamine) in one-pot under ambient conditions gives a series of clusters including Au(C≡CR) (R=-CH-2-F), Au(C≡CR), Au(C≡CR), Au(C≡CR), and Au(C≡CR). These clusters can be well separated via column chromatography.

Deep reinforcement learning in chemistry: A review.

Reinforcement learning (RL) has been applied to various domains in computational chemistry and has found wide-spread success. In this review, we first motivate the application of RL to chemistry and list some broad application domains, for example, molecule generation, geometry optimization, and retrosynthetic pathway search. We set up some of the formalism associated with reinforcement learning that should help the reader translate their chemistry problems into a form where RL can be used to solve them.

Induced chirality at the surface: fixation of a dynamic / invertible helical Co complex on SiO.

Dynamic / invertible helicity was successfully induced at a SiO surface immobilized with a dynamic helical trinuclear cobalt complex, [LCo(NHMe)](OTf), using chiral (() or ())-1-phenylethylamine. Solid-state CD spectra and theoretical calculations suggested that the fixation of the / helical complex on the surface coordination interactions was the key factor of the induced chirality at the surface.

Investigation of the Suzuki-Miyaura cross-coupling reaction on a palladium H-beta zeolite with DFT calculations.

Metal or metal cluster-doped zeolites catalyse a wide variety of reactions. In this work, a coupling reaction between bromobenzene and phenylboronic acid to yield biphenyl with the Pd-H-Beta zeolite catalyst was investigated with density functional theory (DFT) calculations. Utilizing a model system with tetrahedral Pd clusters within the H-Beta zeolite, it was demonstrated that the catalyst exhibited notable reactivity by effectively reducing the activation energy barrier for the reaction.

Element effects in endohedral metal-metal-bonding fullerenes M2@C82 (M = Sc, Y, La, Lu).

Endohedral metal-metal-bonding fullerenes have recently emerged, in which encapsulated metals form a metal-metal bond. However, the physical reasons why some metal elements prefer to form metal-metal bonds inside fullerene are still unclear. Herein, we reported first-principles calculations on electronic structures, bonding properties, dynamics, and thermodynamic stabilities of endohedral metallofullerenes M2@C82 (M = Sc, Y, La, Lu).

Selective synthesis of tightly- and loosely-twisted metallomacrocycle isomers towards precise control of helicity inversion motion.

Molecular twist is a characteristic component of molecular machines. Selectively synthesising isomers with different modes of twisting and controlling their motion such as helicity inversion is an essential challenge for achieving more advanced molecular systems. Here we report a strategy to control the inversion kinetics: the kinetically selective synthesis of tightly- and loosely-twisted isomers of a trinuclear Pd-macrocycle and their markedly different molecular behaviours.

Recent progress in controlling the photoluminescence properties of single-walled carbon nanotubes by oxidation and alkylation.

The functionalization of single-walled carbon nanotubes (SWCNTs) has received considerable attention in the last decade since highly efficient near-infrared photoluminescence (PL) has been observed to be red-shifted compared with the intrinsic PL peak of pristine SWCNTs. The PL wavelength has been manipulated using arylation reactions with aryldiazonium salts and aryl halides. Additionally, simple oxidation and alkylation reactions have proven effective in extensively adjusting the PL wavelength, with the resulting PL efficiency varying based on the chosen reaction techniques and molecular structures.

Mechanistic Studies of Regiocontrolled Bisaddition of Fullerenes Driven by Oriented External Electric Fields.

The challenge of achieving regioselective multifunctionalization on highly symmetric C and C fullerenes persists as a significant hurdle. In this study, we present a novel approach involving the participation of an oriented external electric field (OEEF) to facilitate the regioselective formation of bisadducts in C/C fullerenes. These products are obtained through consecutive Diels-Alder cycloaddition reactions.

Acceleration and deceleration of chirality inversion speeds in a dynamic helical metallocryptand by alkali metal ion binding.

We report that the chirality inversion kinetics of a trinickel(II) cryptand can be controlled by guest recognition in the cryptand cavity. When the guest was absent, the nickel(II) cryptand underwent a dynamic interconversion between the and forms in solution, preferring the form, with a half-life of = 4.99 min.

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation.

Electronic structures of anion-templated silver nanoclusters (Ag NCs) are not well understood compared to conventional, template-free Ag NCs. In this study, we synthesized three new anion-templated Ag NCs, namely [S@Ag(S-4CBM)(PPh)], [S@Ag(S-4CBM)(PPh)], and [Cl@Ag(S-4CBM)(PPh)][PPh], where S-4CBM = 4-chlorobenzene methanethiolate, and single-crystal X-ray crystallography revealed that they have S@Ag, S@Ag, and Cl@Ag cores, respectively. Investigation of their electronic structures by optical spectroscopy and theoretical calculations elucidated the following unique features: (1) their electronic structures are different from those of template-free Ag NCs described by the superatomic concept; (2) optical absorption in the range of 550-400 nm for S-templated Ag NCs is attributed to the charge transitions from S-templated Ag-cage orbitals to the s-shaped orbital in the S moiety; (3) the Cl-templated Ag NCs can be viewed as [Cl@Ag(S-4CBM)(PPh)][PPh] rather than the ion pair [Cl@Ag(S-4CBM)(PPh)][PPh]; and (4) singlet-coupled singly occupied orbitals are involved in the optical absorption of the Cl-templated Ag NC.

Ag Cu (C=CAr) (DPPB) : A Rigid Ligand Co-Protected Bimetallic Silver(I)-Copper(I) Cluster with Room-Temperature Luminescence.

Metal clusters have become increasingly important in various applications, with ligands playing a crucial role in their construction. In this study, we synthesized a bimetallic cluster, Ag Cu (C=CAr) (DPPB) (Ag Cu ), using a rigid acetylene ligand, 3,5-bis(trifluoromethyl)phenylacetylide. Through single-crystal structure characterization, we discovered that the butterfly-shaped Ag Cu motifs were subject to distortion due to steric hindrance imposed by the rigid ligand.

HMGB1 released by mesothelial cells drives the development of asbestos-induced mesothelioma.

Asbestos is the main cause of malignant mesothelioma. Previous studies have linked asbestos-induced mesothelioma to the release of HMGB1 from the nucleus to the cytoplasm, and from the cytoplasm to the extracellular space. In the cytoplasm, HMGB1 induces autophagy impairing asbestos-induced cell death.

Control of functionalized single-walled carbon nanotube photoluminescence competition between thermal rearrangement and elimination.

We conducted the chiral separation of functionalized single-walled carbon nanotubes (SWNTs) with dibromopropane derivatives. Depending on their chirality and diameter, the thermal treatment of functionalized SWNTs leads to a shift in the emission radiation to longer wavelengths owing to rearrangement reaction in competition with elimination reaction.

Selective emergence of photoluminescence at telecommunication wavelengths from cyclic perfluoroalkylated carbon nanotubes.

Chemical functionalisation of semiconducting single-walled carbon nanotubes (SWNTs) can tune their local band gaps to induce near-infrared (NIR) photoluminescence (PL). However, tuning the PL to telecommunication wavelengths (>1300 nm) remains challenging. The selective emergence of NIR PL at the longest emission wavelength of 1320 nm was successfully achieved in (6,5) SWNTs via cyclic perfluoroalkylation.

Photoluminescence control by atomically precise surface metallization of C-centered hexagold(i) clusters using N-heterocyclic carbenes.

The properties of metal clusters are highly dependent on their molecular surface structure. The aim of this study is to precisely metallize and rationally control the photoluminescence properties of a carbon(C)-centered hexagold(i) cluster (CAu) using N-heterocyclic carbene (NHC) ligands with one pyridyl, or one or two picolyl pendants and a specific number of silver(i) ions at the cluster surface. The results suggest that the photoluminescence of the clusters depends highly on both the rigidity and coverage of the surface structure.

Photoluminescence Properties of Single-Walled Carbon Nanotubes Influenced by the Tether Length of Reagents with Two Reactive Sites.

The functionalization of single-walled carbon nanotubes (SWNTs) is an effective method for controlling a local band gap, resulting in photoluminescence (PL) in the near-infrared region. Herein, SWNTs were functionalized using a series of bromoalkanes and dibromoalkanes to evaluate the effects of their length on the nanotube PL properties. When bromoalkanes (C H Br) or dibromoalkanes (C H Br ) with tether lengths of six or more were utilized for six different semiconducting SWNTs, the obtained SWNT adducts exhibited two new PL peaks, whereas dibromoalkanes with tether lengths of 3-5 (C H Br : n=3-5) produced single peaks.

Synergistic Surface Modification of Tin-Lead Perovskite Solar Cells.

Interfaces in thin-film photovoltaics play a pivotal role in determining device efficiency and longevity. In this work, the top surface treatment of mixed tin-lead (≈1.26 eV) halide perovskite films for p-i-n solar cells is studied.

Understanding electronic structures, chemical bonding, and fluxional behavior of Lu@C (2n = 76-88) by a theoretical study.

Endohedral metal-metal-bonding fullerenes, in which encapsulated metals form covalent metal-metal bonds inside, are an emerging class of endohedral metallofullerenes. Herein, we reported quantum-chemical studies on the electronic structures, chemical bonding, and dynamic fluxionality behavior of endohedral metal-metal-bonding fullerenes Lu@C (2n = 76-88). Multiple bonding analysis approaches, including molecular orbital analysis, the natural bond orbital analysis, electron localization function, adaptive natural density partitioning analysis, and quantum theory of atoms in molecules, have unambiguously revealed one two-center two-electron σ covalent bond between two Lu ions in fullerenes.

Inverse design of molecule-metal nanoparticle systems interacting with light for desired photophysical properties.

Molecules close to a metal nanoparticle (NP) have significantly different photophysical properties from those of the isolated one. In order to harness the potential of the molecule-NP system, appropriate design guidelines are required. Here, we propose an inverse design method of the optimal molecule-NP systems and incident electric field for desired photophysical properties.