Probing Out-Of-Plane Charge Transport in Organic Semiconductors Using Conductive Atomic Force Microscopy.

High contact resistance remains the primary obstacle that hinders further advancements of organic semiconductors (OSCs) in electronic circuits. While significant effort has been directed toward lowering the energy barrier at OSC/metal contact interfaces, approaches toward reducing another major contributor to overall contact resistance - the bulk resistance - have been limited to minimizing the thickness of OSC films. However, the out-of-plane conductivity of OSCs, a critical aspect of bulk resistance, has largely remained unaddressed.

Conversion of pyridoxal to pyridoxamine with NH and H on nickel generates a protometabolic nitrogen shuttle under serpentinizing conditions.

Serpentinizing hydrothermal vents are likely sites for the origin of metabolism because they produce H as a source of electrons for CO reduction while depositing zero-valent iron, cobalt, and nickel as catalysts for organic reactions. Recent work has shown that solid-state nickel can catalyze the H-dependent reduction of CO to various organic acids and their reductive amination with H and NH to biological amino acids under the conditions of H-producing hydrothermal vents and that amino acid synthesis from NH, H, and 2-oxoacids is facile in the presence of Ni. Such reactions suggest a metallic origin of metabolism during early biochemical evolution because single metals replace the function of over 130 enzymatic reactions at the core of metabolism in microbes that use the acetyl-CoA pathway of CO fixation.

2025 Roadmap on 3D Nano-magnetism.

The transition from planar (2D) to three-dimensional (3D) magnetic nanostructures represents a significant advancement in both fundamental research and practical applications, offering vast potential for next-generation technologies like ultrahigh-density storage, memory, logic, and neuromorphic computing. Despite being a relatively new field, the emergence of 3D nanomagnetism presents numerous opportunities for innovation, prompting the creation of a comprehensive roadmap by leading international researchers. This roadmap aims to facilitate collaboration and interdisciplinary dialogue to address challenges in materials science, physics, engineering, and computing.

Nonenzymatic Hydration of Phosphoenolpyruvate: General Conditions for Hydration in Protometabolism by Searching Across Pathways.

Numerous reactions within metabolic pathways have been reported to occur nonenzymatically, supporting the hypothesis that life arose upon a primitive nonenzymatic precursor to metabolism. However, most of those studies reproduce individual transformations or segments of pathways without providing a common set of conditions for classes of reactions that span multiple pathways. In this study, we search across pathways for common nonenzymatic conditions for a recurring chemical transformation in metabolism: alkene hydration.

Photo-Accelerated Synthesis of Oligo(triazole amide)s.

A photo-assisted process is explored for improving the synthesis of oligo(triazole amide)s, which are prepared by solid phase synthesis using a repeated cycle of two reactions: amine-carboxylic acid coupling and copper-catalyzed azide-alkyne cycloaddition (CuAAC). The improvement of the second reaction is investigated herein. A catalytic system involving Cu(II)Cl, N,N,N',N″,N″-pentamethyldiethylenetriamine (PMDETA) and a titanocene photoinitiator is explored for reducing the reaction time of CuAAC.

Open quantum dynamics with variational non-Gaussian states and the truncated Wigner approximation.

We present a framework for simulating the open dynamics of spin-boson systems by combining variational non-Gaussian states with a quantum trajectories approach. We apply this method to a generic spin-boson Hamiltonian that has both Tavis-Cummings and Holstein type couplings and which has broad applications to a variety of quantum simulation platforms, polaritonic physics, and quantum chemistry. Additionally, we discuss how the recently developed truncated Wigner approximation for open quantum systems can be applied to the same Hamiltonian.

Triflic Acid-Catalyzed Dehydrative Amination of 2-Arylethanols with Weak N-Nucleophiles in Hexafluoroisopropanol.

The catalytic deoxyamination of readily available 2-arylethanols offers an appealing, simple, and straightforward means of accessing β-(hetero)arylethylamines of biological interest. Yet, it currently represents a great challenge to synthetic chemistry. In most cases, the alcohol has to be either pre-activated in situ or converted into a reactive carbonyl intermediate, limiting the substrate scope for some methods.

Coenzymes in a pre-enzymatic metabolism.

Experiments now support theoretical suggestions that coenzymes mediated key metabolic reactions before the emergence of enzymes. Three coenzymes believed essential to the core metabolism of the last universal common ancestor to extant life (pyridoxal phosphate, adenosine diphosphate, and nicotinamide adenine dinucleotide) were recently found to be active in their corresponding metabolic reactions in the absence of enzymes. These findings suggest an earlier contribution of coenzymes to abiogenesis, ultimately yielding insights into the prebiotic origins of metabolism.

Defect-engineering of liquid-phase exfoliated 2D semiconductors: stepwise covalent growth of electronic lateral hetero-networks.

Two-dimensional (2D) in-plane heterostructures display exceptional optical and electrical properties well beyond those of their pristine components. However, they are usually produced by tedious and energy-intensive bottom-up growth approaches, not compatible with scalable solution-processing technologies. Here, we report a new stepwise microfluidic approach, based on defect engineering of liquid-phase exfoliated transition metal dichalcogenides (TMDs), to synthesize 2D hetero-networks.

A povarov-type reaction to access tetrahydroquinolines from -benzylhydroxylamines and alkenes in HFIP.

Here, we report the synthesis of tetrahydroquinolines between newly developed -benzylhydroxylamine reagents and alkenes using HFIP as a solvent. This transformation is notably applicable to highly electronically deactivated styrenes and aliphatic alkenes, expanding the range of tetrahydroquinolines attainable.

Engineering the Interfacing of Molecules with 2D Transition Metal Dichalcogenides: Enhanced Multifunctional Electronics.

ConspectusEngineering all interfaces between different components in electronic devices is the key to control and optimize fundamental physical processes such as charge injection at metal-semiconductor interfaces, gate modulation at the dielectric-semiconductor interface, and carrier modulation at semiconductor-environment interfaces. The use of two-dimensional (2D) crystals as semiconductors, by virtue of their atomically flat dangling bond-free structures, can facilitate the tailoring of such interfaces effectively. In this context, 2D transition metal dichalcogenides (TMDs) have garnered tremendous attention over the past two decades owing to their exclusive and outstanding physical and chemical characteristics such as their strong light-matter interactions and high charge mobility.

Complex Sequence-Defined Heteropolymers Enable Controlled Film Growth in Layer-By-Layer Assembly.

Digitally-encoded poly(phosphodiesters) (d-PPDE) with highly complex primary structures are evaluated for layer-by-layer (LbL) assembly. To be easily decoded by mass spectrometry (MS), these digital polymers contain many different monomers: 2 coding units allowing binary encryption, 1 cleavable spacer allowing controlled MS fragmentation, and 3 mass tags allowing fragment identification. These complex heteropolymers are therefore composed of 6 different motifs.

Iron(II)-Catalyzed 1,2-Diamination of Styrenes Installing a Terminal NH Group Alongside Unprotected Amines.

1,2-Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods are usually limited in scope and produce diamines where one or both nitrogens are protected, adding synthetic steps for deprotection and further N-functionalization to reach a desired target. Furthermore, the range of amino groups that can be introduced at the internal position is fairly limited.

Rational Construction of Two-Dimensional Conjugated Metal-Organic Frameworks (2D c-MOFs) for Electronics and Beyond.

ConspectusTwo-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a novel class of multifunctional materials, attracting increasing attention due to their highly customizable chemistry yielding programmable and unprecedented structures and properties. In particular, over the past decade, the synergistic relationship between the conductivity and porosity of 2D c-MOFs has paved the way toward their widespread applications. Despite their promising potential, the majority of 2D c-MOFs have yet to achieve atomically precise crystal structures, hindering the full understanding and control over their electronic structure and intrinsic charge transport characteristics.

Difunctionalization Processes Enabled by Hexafluoroisopropanol.

In the past 5 years, hexafluoroisopropanol (HFIP) has been used as a unique solvent or additive to enable challenging transformations through substrate activation and stabilization of reactive intermediates. In this Review, we aim at describing difunctionalization processes which were unlocked when HFIP was involved. Specifically, we focus on cyclizations and additions to alkenes, alkynes, epoxides, and carbonyls that introduce a wide range of functional groups of interest.

A prebiotic Krebs cycle analog generates amino acids with H and NH over nickel.

Hydrogen (H) has powered microbial metabolism for roughly 4 billion years. The recent discovery that it also fuels geochemical analogs of the most ancient biological carbon fixation pathway sheds light on the origin of metabolism. However, it remains unclear whether H can sustain more complex nonenzymatic reaction networks.

Cycloheptatrienyl-Bridged Triple-Decker Complexes.

The first structurally characterized organometallic multidecker sandwich complexes featuring a cycloheptatrienyl ring (Cht, CH) in the coordination sphere are presented. The synthesis of inverse sandwich complexes of the rare earth elements Y and Er with a bridging cycloheptatrienyl ligand of the type [(thf)(BH)Ln(μ-η:η-Cht)Ln(BH)(thf)] is described first. The subsequent introduction of the Cot ligand (Cot = 1,4-(PrSi)CH) into the coordination sphere of the rare earth cations resulted in the isolation of unprecedented triple-decker compounds with the formula [(thf)K{(η-Cot)Ln}(μ-η:η-Cht)], bearing a seven-membered aromatic carbon ring as a middle deck.

Yb-to-Eu Cooperative Sensitization Upconversion in a Multifunctional Molecular Nonanuclear Lanthanide Cluster in Solution.

Lanthanide metal clusters excel in combining molecular and material chemistry properties. Here, we report an efficient cooperative sensitization UC phenomenon of a Eu/Yb nonanuclear lanthanide cluster in CDOD. The synthesis and characterization of the heteronuclear cluster in the solid state and solution are described together with the UC phenomenon showing Eu luminescence in the visible region upon 980 nm NIR excitation of Yb at concentrations as low as 100 nM.

Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics.

Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K(DEDBA)] and [Ln(η-Cot)(BH)(thf)] (Cot=1,4-(PrSi)CH) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η-Cot)Ln(η-DEDBA)] (Ln=Y, Dy, Er).

"The Sulfur Dance" Around Arenes and Heteroarenes - the Reversible Nature of Nucleophilic Aromatic Substitutions.

We disclose the features of a category of reversible nucleophilic aromatic substitutions in view of their significance and generality in dynamic aromatic chemistry. Exchange of sulfur components surrounding arenes and heteroarenes may occur at 25 °C, in a process that one may call a "sulfur dance". These SAr systems present their own features, apart from common reversible reactions utilized in dynamic covalent chemistry (DCC).

It's not just the size that matters: crystal engineering of lanthanide-based coordination polymers.

Synthesis and characterization of Lewis base free coordination polymers of selected lanthanides are presented. For this purpose, the substituted Cot ligand (Cot = 1,4-bis-triisopropylsilyl-cyclo-octatetraendiide) was used to synthesize homoleptic, anionic multidecker compounds of the type [K{Ln(ɳ-Cot)}]. Depending on the solvent used for crystallization and the ionic radii of the lanthanide cations, three different categories of one-dimensional heterobimetallic coordination polymers were obtained in the solid state.

Tunable Charge Transport and Spin Dynamics in Two-Dimensional Conjugated Metal-Organic Frameworks.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits.

Rapid Access to Densely Functionalized Cyclopentenyl Sulfoximines through a Sc-Catalyzed Aza-Piancatelli Reaction.

Sulfoximines make up a class of compounds of growing interest for crop science and medicinal chemistry, but methods for directly incorporating them into complex molecular scaffolds are lacking. Here we report a scandium-catalyzed variant of the aza-Piancatelli cyclization that can directly incorporate sulfoximines as nucleophiles rather than the classical aniline substrates. Starting from 2-furylcarbinols and sulfoximines, the reaction provides direct access to 4-sulfoximinocyclopentenones, a new scaffold bearing cyclopentenone and sulfoximine motifs, both of interest for bioactive compounds.