Unprecedented short-circuit current density and efficiency of vacuum-deposited organic solar cells based on 8H-thieno[2',3':4,5]thieno[3,2-b] thieno[2,3-d]pyrrole.

Despite the many advantages for industrial mass production, vacuum-deposited organic solar cells (OSCs) suffer from low efficiency, primarily due to the limited molecular library of small-molecule donor and acceptor materials, which remains a significant challenge. Herein, two donor-acceptor-acceptor (D-A-A)-configured small-molecule donors, named TTBTDC and TTBTDC-F were synthesized, using 8H-thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]pyrrole (TTP) as a new fused-ring donor unit. Benefiting from the strong electron-donating ability of the TTP moiety and the adoption of the D-A-A molecular configuration, these molecules exhibited strong visible and near-infrared absorption as well as deep-lying highest occupied molecular orbital (HOMO) energy levels.

A Pyrrole-Fused Nanographene and its Edge-Perchlorinated Derivative Featuring a Corannulene Core and Five N-doped Heptagons.

A pyrrole-fused analogue of warped nanographene, designated as deca-nitrogen doped 'WNG' (azaWNG), was synthesized through the annular fusion of decapyrroylcorannulene. The resulting azaWNG exhibited extremely limited solubility in common organic solvents and was characterized solely by mass spectrometry. Theoretical calculations revealed that azaWNG has a sunflower-like molecular structure with electron-deficient corannulene as the core and electron-rich pyrrole as the petals, demonstrating a significantly narrower energy gap compared to all-carbon WNG.

Corannulene-Based Quintuple [6]/[7]Helicenes: Well-Preserved Bowl Core, Inhibited Bowl Inversion and Supramolecular Assembly with Fullerenes.

Herein, corannulene-based quintuple [6]helicenes (Q[6]H-1 and Q[6]H-2) and [7]helicene (Q[7]H) were synthesized via penta-fold Heck and Mallory reaction. Notably, Q[7]H represents the highest reported helicene based on corannulene. X-ray crystallography reveals that Q[6]H-2 adopts a propeller-shaped conformation with a well-preserved corannulene core, while Q[6]H-1 and Q[7]H exhibit quasi-propeller-shaped conformations.

Bottom-up construction of chiral metal-peptide assemblies from metal cluster motifs.

The exploration of artificial metal-peptide assemblies (MPAs) is one of the most exciting fields because of their great potential for simulating the dynamics and functionality of natural proteins. However, unfavorable enthalpy changes make forming discrete complexes with large and adaptable cavities from flexible peptide ligands challenging. Here, we present a strategy integrating metal-cluster building blocks and peptides to create chiral metal-peptide assemblies and get a family of enantiopure [R-/S-NiL] (n = 2, 3, 6) MPAs, including the R-/S-NiL capsule, the S-NiL trigonal prism, and the R-/S-NiL octahedron cage.

Structurally Compact Penta(N,N-diphenylamino)corannulene as Dopant-free Hole Transport Materials for Stable and Efficient Perovskite Solar Cells.

Hole transport materials (HTMs) are essential for improving the stability and efficiency of perovskite solar cells (PSCs). In this study, we have designed and synthesized a novel organic small molecule HTM, cor-(DPA), characterized by a bowl-shaped core with symmetric five diphenylamine groups. Compared to already-known HTMs, the bowl-shaped and relatively compact structure of cor-(DPA) facilitates intermolecular π-π interactions, promotes film formations, and enhances charge transport.

Enhancing the performance of molecule-based piezoelectric sensors by optimizing their microstructures.

By combining the rigidity of inorganic components with the flexibility of organic components, molecule-based ferroelectrics emerge as promising candidates for flexible, self-powered piezoelectric sensors. While it is well known that the performance of piezoelectric sensor devices depends not only on the materials' piezoelectric properties but also on the device architecture, research into enhancing molecule-based piezoelectric sensor performance through microstructure optimization has never been investigated. Here, we report the synthesis of a molecule-based ferroelectric, [(2-bromoethyl) trimethylammonium][GaBr] ([(CH)NCHCHBr][GaBr]) (1), which exhibits a piezoelectric coefficient ( ) of up to 331 pC N.

Ln/Cu Bimetallic Nanoclusters with Enhanced NIR-II Luminescence.

Coinage-metal clusters with excellent luminescence properties have attracted considerable interest due to their intriguing structures and potential applications. However, achieving strong near-infrared (NIR) luminescence in these clusters is highly challenging. Here, we have successfully synthesized the first Ln/Cu bimetallic clusters, formulated as [LnCuOCl(2-MeO-PhC≡C)] (ClO) (Ln = Yb for , Er for , and Gd for ).

Decafluorinated and Perfluorinated Warped Nanographenes: Synthesis, Structural Analysis, and Properties.

Fluorination is a useful approach for tailoring the physicochemical properties of nanocarbon materials. However, owing to the violent reactivity of fluorination, achieving edge-perfluorination of nanographene while maintaining its original π-conjugated structure is challenging. Instead of using traditional fluorination, here, we employed a bottom-up strategy involving fluorine preinstallation and synthesized decafluorinated and perfluorinated warped nanographenes ( and , respectively) through a 10-fold Suzuki-Miyaura coupling followed by a harsh Scholl reaction, whereby precisely edge-perfluorinated nanographene with an intact π-conjugated structure was achieved for the first time.

Achievement of a giant electromechanical conversion coefficient in a molecule-based ferroelectric.

Molecule-based ferroelectrics are promising candidates for flexible self-powered power supplies (, piezoelectric generators (PEGs)). Although the large electromechanical conversion coefficients ( × ) of piezoelectrics are key to enhancing the performance of PEGs in their nonresonant states, it remains a great challenge to obtain molecule-based piezoelectrics with large × . Here, we report a molecule-based ferroelectric [(CH)NCHCHCl][GaBr] (1) that exhibits the largest piezoelectric coefficient (∼454 pC N) and electromechanical conversion coefficient (4953.

Strong NIR-II Magneto-Optical Activity of a Chiral SmCu Cage.

The magneto-optical response of chiral materials holds significant potential for applications in physics, chemistry, and biology. However, exploration of the near-infrared (NIR) magneto-optical response remains limited. Herein, we report the synthesis and strong NIR-II magneto-optical activity of three pairs of chiral 34 clusters of (Ln = Sm, Gd, and Dy).

High-Nuclearity LnAl Clusters: Neonates of Open Hollow Dodecahedral Cage Families.

Open hollow dodecahedral cage clusters have long been a coveted target in synthetic chemistry, yet their creation poses immense challenges. Here we report two open hollow dodecahedral lanthanide-aluminum (Ln-Al) heterometallic cage clusters, namely, [LnAl(μ-OH)(μ-OH)(OAc)(HO)](ClO)·(MeCN)·(HO), (Ln = Dy and = 27, = 300 for ; Ln = Y and = 28, = 420 for ). Remarkably, the 350 metal atoms in and display a Keplerate-type four-shell structure of truncated icosidodecahedron@dodecahedron@dodecahedron@icosidodecahedron.

Design and Performance of Small-Molecule Donors with Donor-π-Acceptor Architecture Toward Vacuum-Deposited Organic Photovoltaics Having Heretofore Highest Short-Circuit Current Density.

The development of high-performance organic photovoltaic materials is of crucial importance for the commercialization of organic solar cells (OSCs). Herein, two structurally simple donor-π-conjugated linker-acceptor (D-π-A)-configured small-molecule donors with methyl-substituted triphenylamine as D unit, 1,1-dicyanomethylene-3-indanone as A unit, and thiophene or furan as π-conjugated linker, named DTICPT and DTICPF, are developed. DTICPT and DTICPF are facilely prepared via a two-step synthetic process with simple procedures.

Achieving Magnetic Refrigerants with Large Magnetic Entropy Changes and Low Magnetic Ordering Temperatures.

Adiabatic demagnetization refrigeration (ADR) is a promising cooling technology with high efficiency and exceptional stability in achieving ultralow temperatures, playing an indispensable role at the forefront of fundamental and applied science. However, a significant challenge for ADR is that existing magnetic refrigerants struggle to concurrently achieve low magnetic ordering temperatures () and substantial magnetic entropy changes (-Δ) at ultralow temperatures. In this work, we propose the combination of Gd and Yb to effectively regulate both -Δ and in ultralow temperatures.

pH-Driven Rotational Configuration of Keggin-Fe Clusters and Their Transformations.

Keggin-Fe clusters are considered foundational building blocks or prenucleation precursors of ferrihydrite. Understanding the factors that influence the rotational configuration of these clusters, and their transformations in water, is vital for comprehending the formation mechanism of ferrihydrite. Here, we report syntheses and crystal structures of four lanthanide-iron-oxo clusters, namely, [DyFe(Gly)(μ-OH)(μ-OH)(μ-O)(HO)]·13ClO·19HO (), [DyFe(Gly)(μ-OH)(μ-O)(HO)]·13ClO·14HO (), [PrFe(Gly)(μ-OH)(μ-O)(μ-O)(HO)]·6ClO·20HO (), and [PrFe(Gly)(μ-OH)(μ-O)(HO)]·13ClO·22HO (, Gly = glycine).

Accurate Prediction of the Magnetic Ordering Temperature of Ultralow-Temperature Magnetic Refrigerants.

Adiabatic demagnetization refrigeration is known to be the only cryogenic refrigeration technology that can achieve ultralow temperatures (≪1 K) at gravity-free conditions. The key indexes to evaluate the performance of magnetic refrigerants are their magnetic entropy changes (-Δ) and magnetic ordering temperature (). Although, based on the factors affecting the -Δ of magnetic refrigerants, one has been able to judge if a magnetic refrigerant has a large -Δ, how to accurately predict their remains a huge challenge due to the fact that the of magnetic refrigerants is related to not only magnetic exchange but also single-ion anisotropy and magnetic dipole interaction.

Enhancement of Magneto-Chiral Dichroism Intensity by Chemical Design: The Key Role of Magnetic-Dipole Allowed Transitions.

Here we report on the strong magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption up to 5.0 T on {ErNi} metal clusters obtained by reaction of enantiopure chiral ligands and Ni and Er precursors. Single-crystal diffraction analysis reveals that these compounds are 34 heterometallic clusters, showing helical chirality.

Magneto-optical Properties of Chiral CoLn and CoLn (Ln = Dy and Er) Clusters.

A series of chiral heterometallic Ln-Co clusters, denoted as and (Ln = Dy and Er), were synthesized by reacting the chiral chelating ligand (/)-2-(1-hydroxyethyl)pyridine (Hmpm), CoAc·4HO, and Ln(NO)·6HO. and exhibit perfect mirror images in circular dichroism within the 320-700 nm range. Notably, the and clusters display pronounced magnetic circular dichroism (MCD) responses of the hypersensitive f-f transitions I-G at 375 nm and I-H at 520 nm of Er ions.

Tuning Electrocatalytic Water Oxidation Activity: Insights from the Active-Site Distance in LnCu Clusters.

Atomically precise metal clusters serve as a unique model for unraveling the intricate mechanism of the catalytic reaction and exploring the complex relationship between structure and activity. Herein, three series of water-soluble heterometallic clusters LnCu, abbreviated as LnCu-AC (Ln = La, Nd, Gd, Er, Yb; HAC = acetic acid), LnCu-IM (Ln = La and Nd; IM = Imidazole), and LnCu-IDA (Ln = Nd; HIDA = Iminodiacetic acid) are presented, each featuring a uniform metallic core stabilized by distinct protected ligands. Crystal structure analysis reveals a triangular prism topology formed by six Cu ions around one Ln ion in LnCu, with variations in Cu···Cu distances attributed to different ligands.

Single-molecule magnet behavior in heterometallic decanuclear [LnFe] (Ln = Y, Dy, Ho, Tb, Gd) coordination clusters.

Five decanuclear lanthanide-iron clusters, formulated as [LnFe(hmp)(μ-OH)(μ-OH)(μ-O)(HO)]·6ClO·HO ( ≈ 8, Ln = Y for 1; ≈ 6, Ln = Dy for 2; ≈ 6, Ln = Ho for 3; ≈ 7, Ln = Tb for 4; ≈ 7, Ln = Gd for 5, Hhmp = 2-(hydroxymethyl)pyridine), have been synthesized and structurally characterized. Single-crystal structural analysis reveals that the cluster consists of six face-sharing defective cubane units. Dynamic magnetic investigations indicated that cluster 2 exhibits single-molecule magnet behavior under a zero dc field eliciting an effective energy barrier of = 17.

Soluble GdCu clusters: effective molecular electrocatalysts for water oxidation.

The water oxidation half reaction in water splitting for hydrogen production is extremely rate-limiting. This study reports the synthesis of two heterometallic clusters (GdCu-IM and GdCu-AC) for application as efficient water oxidation catalysts. Interestingly, the maximum turnover frequency of GdCu-IM in an NaAc solution of a weak acid (pH 6) was 319 s.

A Doped Lanthanide-Based Coordination Polymer Exhibiting High Relative Sensitivity to Ratiometric Luminescent Thermometers at 440 K.

Ratiometric luminescent thermometers with excellent performance often require the luminescent materials to possess high thermal stability and relative sensitivity (). However, such luminescent materials are very rare, especially in physiological (298-323 K) and high-temperature (>373 K) regions. Here we report the synthesis and luminescent property of [TbEu(pfbz)(phen)Cl] (), which not only exhibits high in physiological temperature but also has a up to 7.

Exploration and Insights on Topology Adjustment of Giant Heterometallic Cages Featuring Inorganic Skeletons Assisted by Machine Learning.

Inorganic molecular cages are emerging multifunctional molecular-based platforms with the unique merits of rigid skeletons and inherited properties from constituent metal ions. However, the sensitive coordination bonds and vast synthetic space have limited their systematic exploration. Herein, two giant cage-like clusters featuring the organic ligand-directed inorganic skeletons of Ni[LaNi(IDA)(OH)(CO)(HO)]·(NO)·(HO) (, 5 × 5 × 3 - CO) and [LaNi(IDA)(OH)(CO)(NO)(HO)]·(NO)·(HO) (, 5 × 5 × 5 - CO) were discovered by a high-throughput synthetic search.

Uranyl Polyoxotungstate Cluster for Visible-Light-Driven Heterogeneous C-H Selective Fluorination.

The selective fluorination of C-H bonds at room temperature using heterogeneous visible-light catalysts is both interesting and challenging. Herein, we present the heterogeneous sandwich-type structure uranyl-polyoxotungstate cluster Na{Na@[(SbWO)(UO)(POOH)]}·46HO (denoted as ) to regulate the selective fluorination of the C-H bond under visible light and room temperature. This is the first report in which uranyl participates in the fluorination reaction in the form of an insoluble substance.

From Helices to Crystals: Multiscale Representation of Chirality in Double-Helix Structures.

Single crystals with chiral shapes aroused the interest of chemists due to their fascinating polarization rotation properties. Although the formation of large-scale spiral structures is considered to be a potential factor in chiral crystals, the precise mechanism behind their formation remains elusive. Herein, we present a rare phenomenon involving the multitransfer and expression of chirality at micro-, meso-, and macroscopic levels, starting from chiral carbon atoms and extending to the double-helical secondary structure, ultimately resulting in the chiral geometry of crystals.

Correction: Multiple correlations between spin crossover and fluorescence in a dinuclear compound.

Correction for 'Multiple correlations between spin crossover and fluorescence in a dinuclear compound' by Chun-Feng Wang , , 2016, , 14322-14325, https://doi.org/10.1039/C6CC07810A.