Synthesis and characterization of Craig-type antiaromatic species with [4n + 2] π electrons.

Antiaromaticity is extended from aromaticity as a complement to describe the unsaturated cyclic molecules with antiaromatic destabilization. To prepare antiaromatic species is a particularly challenging goal in synthetic chemistry because of the thermodynamic instability of such molecules. Among that, both Hückel and Möbius antiaromatic species have been reported, whereas the Craig one has not been realized to date. Here, we report the first example of planar Craig antiaromatic species. Eight Craig antiaromatic compounds were synthesized by deprotonation-induced reduction process and were fully characterized as follows. Single-crystal X-ray crystallography showed that these complexes have planar structures composed of fused five-membered rings with clearly alternating carbon-carbon bond lengths. In addition, proton NMR (1H NMR) spectroscopy in these structures showed distinctive upfield shifts of the proton peaks to the range of antiaromatic peripheral hydrogens. Experimental spectroscopy observations, along with density-functional theory (DFT) calculations, provided evidence for the Craig antiaromaticity of these complexes. Further study experimentally and theoretically revealed that the strong exothermicity of the acid-base neutralization process was the driving force for this challenging transformation forming Craig antiaromatic species. Our findings complete a full cycle of aromatic chemistry, opening an avenue for the development of new class of antiaromatic systems.

Conjugated polymers based on metalla-aromatic building blocks.

Conjugated polymers usually require strategies to expand the range of wavelengths absorbed and increase solubility. Developing effective strategies to enhance both properties remains challenging. Herein, we report syntheses of conjugated polymers based on a family of metalla-aromatic building blocks via a polymerization method involving consecutive carbyne shuttling processes. The involvement of metal d orbitals in aromatic systems efficiently reduces band gaps and enriches the electron transition pathways of the chromogenic repeat unit. These enable metalla-aromatic conjugated polymers to exhibit broad and strong ultraviolet-visible (UV-Vis) absorption bands. Bulky ligands on the metal suppress π-π stacking of polymer chains and thus increase solubility. These conjugated polymers show robust stability toward light, heat, water, and air. Kinetic studies using NMR experiments and UV-Vis spectroscopy, coupled with the isolation of well-defined model oligomers, revealed the polymerization mechanism.

Unique Properties and Emerging Applications of Carbolong Metallaaromatics.

ConspectusAromatic compounds are important in synthetic chemistry, biomedicines, and materials science. As a special type of aromatic complex, transition-metal-based metallaaromatics contain at least one transition metal in an aromatic framework. The chemistry of metallaaromatics has seen much progress in computational studies and synthetic methods, but their properties and applications are still emerging. In recent years, we have disclosed a series of metal-centered conjugated polycyclic metallacycles in which a carbon chain is chelated to a metal center through at least three metal-carbon bonds. These are termed carbolong complexes and exhibit good stability to water, oxygen, light, and heat on account of their polydentate chelation and aromaticity, making them easy to handle. Carbolong complexes are not only special π-conjugated aromatics but also organometallics; therefore, they have the properties of both species. In this Account, we showcase the recent advances in their applications based on their different properties.First, carbolong complexes are a special kind of π-conjugated aromatic, with the ability to transmit electrons, allowing them to function as single-molecule conductors and candidates for electron transporting layer materials (ETLs) in solar cells. A series of carbolong complexes have been proved to be useful as achievable ETLs which enhance device performance in both organic solar cells and perovskite solar cells.Second, due to the involvement of d orbitals in the conjugation, carbolong complexes normally exhibit strong and broad absorption, even in some cases extending to the near-infrared region (NIR). The absorbed optical energy can be converted into light, heat, and ultrasound; consequently, carbolong compounds can be used as core moieties in smart materials. For example, 7C carbolong complexes were found to exhibit aggregation-enhanced near-infrared emission (AIEE). Some 12C carbolong complexes have been designed into the core moieties of NIR-responsive polymers, such as cylindrical NIR-responsive materials, self-healing materials, and shape memory materials. In contrast to the stereotypically toxic osmium compounds such as the highly toxic OsO4, some osmium carbolong complexes exhibit low cell cytotoxicity and good biocompatibility; consequently, they also have potential applications in the biomedical area. For example, benefiting from broad absorption in the NIR, 9C and 12C carbolong complexes have been used in photoacoustic imaging and photothermal therapy, respectively. In addition, photodynamic therapeutic applications which take advantage of a carbolong peroxo complex are discussed.Third, as special transition-metal complexes chelated by carbon-based ligands, a carbolong peroxo complex has displayed catalytic activity in the dehydrogenation of alcohols and a bimetallic carbolong complex has been used to catalyze difunctionalization reactions of unactivated alkenes.Overall, aromatic carbolong complexes have been applied to photovoltaics, smart materials, phototherapy, and catalytic reactions. Moving forward, we hope that this Account will shed light on future studies and theoretical research and encourage more discoveries of the properties of other metallaaromatics.

Electrophilic aromatic substitution reactions of compounds with Craig-Möbius aromaticity.

Electrophilic aromatic substitution (EAS) reactions are widely regarded as characteristic reactions of aromatic species, but no comparable reaction has been reported for molecules with Craig-Möbius aromaticity. Here, we demonstrate successful EAS reactions of Craig-Möbius aromatics, osmapentalenes, and fused osmapentalenes. The highly reactive nature of osmapentalene makes it susceptible to electrophilic attack by halogens, thus osmapentalene, osmafuran-fused osmapentalene, and osmabenzene-fused osmapentalene can undergo typical EAS reactions. In addition, the selective formation of a series of halogen substituted metalla-aromatics via EAS reactions has revealed an unprecedented approach to otherwise elusive compounds such as the unsaturated cyclic chlorirenium ions. Density functional theory calculations were conducted to study the electronic effect on the regioselectivity of the EAS reactions.

Craig-Hückel Hybrid Aromatic Metalla-dehydro[11]annulenes Constructed by a Formal [10+1] Cycloaddition Reaction.

Aromatic metalla-annulenes are important aromatic compounds, research into which has been mainly concentrated on metal-benzenes and their lower homologues. Reports on their superior homologs are rare, and this has greatly limited the systematic study of their properties. In this work, a series of osma-dehydro[11]annulenes with good air and thermal stability were prepared in high yields through a simple [10+1] strategy, by incorporating a metal fragment into conjugated ten-carbon chains in a one-pot reaction. They are the first monometallic aromatic metalla-[n]annulenes with the ring size larger than 6, and their Craig-Hückel hybrid aromaticity is supported by various physical and computational parameters. Besides, these complexes show versatile reactivities, not only giving further evidence for their aromaticity, but also demonstrating their physical and chemical properties can easily be regulated. This work enriches the metalla-aromatic chemistry, and provides a new avenue for the synthesis of large metalla-annulenes with different ring sizes.

Isolation, Reactivity, and Tunable Properties of a Strained Antiaromatic Osmacycle.

Strain and antiaromaticity in compounds are recognized as two substantial destabilizing features, and consequently, realization of dual destabilizing features in a single molecule is challenging and far more difficult in a single ring. Moreover, transformation of an antiaromatic framework to different antiaromatic or aromatic species is a significant subject in antiaromatic chemistry and has attracted increasing interest. In this work, we isolated a highly strained antiaromatic metallacycle in which a cyclic metal vinylidene unit is embedded. Computational studies revealed its ring strain energies and antiaromatic character and showed that the metal incorporation and the phosphonium substituents play a crucial role in its stabilization. The mechanism of its formation has been illustrated by density functional theory (DFT) calculations and the isolation of a key intermediate. We further discovered diverse reactivities and structural reshuffling of this unusual strained antiaromatic complex according to its two destabilizing characters. We obtained two isomers of metallaindenes fused with oxiranes from the direct oxidation of the metal vinylidene or by nucleophilic addition to an isolated metallacyclocumulene formed by the reaction of metal vinylidene with hydroxide ion, achieving a reconfiguration of the antiaromatic framework. Transformations of the antiaromatic metallacycle by electrophiles to various aromatic metallaindynes have been achieved, and that a condensed Fukui function was employed to confirm the regioselectivity of the electrophilic additions, and the acid/base-induced aromaticity switch along with tunable photophysical properties were investigated. These interesting transformations not only enrich the chemistry of metal vinylidenes and antiaromatics and could also perform potentially as switchable optical materials.

Stereoelectronic Modulation of a Single-Molecule Junction through a Tunable Metal-Carbon dπ-pπ Hyperconjugation.

Conjugated molecules play a critical role in the construction of single-molecule devices. However, most conventional conjugated molecules, such as hydrocarbons, involve only a pπ-pπ conjugation of light elements. While the metal d-orbitals can introduce abundant electronic effects to achieve novel electronic properties, it is very scarce for the charge transport study of dπ-pπ conjugated pathways with a metal involved. Here, we employed the single-molecule break junction technique to investigate the charge transport through dπ-pπ conjugated backbones with metal-carbon multiple bonds integrated into the alternative conjugated pathways. The involved dπ-pπ conjugation not only supports high conductivity comparable to that of conjugated hydrocarbons but also significantly enhances the tunable diversity in electronic properties through the metal-induced secondary interaction. Specifically, the introduction of the metal brings an unconventionally stereoelectronic effect triggered by metal-carbon dπ-pπ hyperconjugation, which can be tuned by protonation taking place on the metal-carbon multiple bonds, collectively modulating the single-molecule rectification feature and transmission mechanism. This work demonstrates the promise of utilizing the diverse electronic effect of metals to design molecular devices.

Synthesis and Optoelectronic Applications of dπ -pπ Conjugated Polymers with a Di-metallaaromatic Acceptor.

The development of conjugated polymers especially n-type polymer semiconductors is powered by the design and synthesis of electron-deficient building blocks. Herein, a strong acceptor building block with di-metallaaromatic structure was designed and synthesized by connecting two electron-deficient metallaaromatic units through a π-conjugated bridge. Then, a double-monomer polymerization methodology was developed for inserting it into conjugated polymer scaffolds to yield metallopolymers. The isolated well-defined model oligomers indicated polymer structures. Kinetic studies based on nuclear magnetic resonance and ultraviolet-visible spectroscopies shed light on the polymerization process. Interestingly, the resulted metallopolymers with dπ -pπ conjugations are very promising electron transport layer materials which can boost photovoltaic performance of an organic solar cell, with power conversion efficiency up to 18.28 % based on the PM6 : EH-HD-4F non-fullerene system. This work not only provides a facile route to construct metallaaromatic conjugated polymers with various functional groups, but also discovers their potential applications for the first time.

Selective Difunctionalization of Unactivated Aliphatic Alkenes Enabled by a Metal-Metallaaromatic Catalytic System.

The design of organometallic catalysts is crucial in the development of catalytic reactions. Herein, we describe a heterometallic [Os-Cu] complex with the characteristics of bimetallics, metallaaromatics, and pincer complexes. This complex serves as a highly effective catalyst for selective amino- and oxyselenation of unactivated alkenes. More than 80 examples including challenging substrates of unsymmetric aliphatic alkenes and amine-based nucleophiles in such reactions are provided. These reactions produce 1,2-difunctionalized products with good yields and high levels of chemo-, regio-, and stereoselectivity. Our studies revealed the following: (i) The usually inert osmium center activates the N- or O-centered nucleophiles. (ii) The copper-osmium bonding and its cooperative effects play essential roles in control the selectivity by bringing the reaction components into close proximity. (iii) The metallaaromatic moiety helps to stabilize the intermediate. These findings provide a versatile platform for catalyst design based on metal-metallaaromatic cooperative effects that have not been attained previously with bimetallic complexes.

One-Pot Synthesis of High-Strained Metal Vinylidene and Metal Carbyne.

A novel one-pot reaction producing a metal vinylidene structure in a five-membered ring by cyclization of a multiyne has been achieved. The ring strain and the high stability of the cyclic metal vinylidene complexes have been analyzed experimentally and computationally. The metal vinylidene unit in a fused-ring complex is unreactive to both nucleophiles and electrophiles. It reacts however at the nearby carbonyl group achieving the unprecedented conversion of metal tributing factors for the aromaticity-driven process has been studied by DFT calculations.

Metallaaromatic Chemistry: History and Development.

Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.

Condensed Osmaquinolines with NIR-II Absorption Synthesized by Aryl C-H Annulation and Aromatization.

The structural design and tuning of properties of metallaaromatics are crucial in materials and energy science. Herein, we describe the rapid synthesis of tetracyclic metallaaromatics containing quinoline and pentalene motifs fused by a metal-bridged fragment. These unique compounds display remarkably broad absorption, enabling for the first time the absorption of metallaaromatics to reach the second near-infrared (NIR-II) bio-window. The formation of osmaquinoline unit involves an unconventional C(sp2 )-C(sp3 ) coupling promoted by AgBF4 to achieve [3+3] cycloaddition. The introduction of cyclic dπ -pπ conjugation and extension of the aromatic π-framework can effectively shrink the HOMO-LUMO gap, thus broadening the absorption window. The considerable photothermal conversion efficiency (PCE) in both the NIR-I and NIR-II windows, the high photothermal stability and the excellent electrochemical behavior suggest many potential applications of these condensed metallaquinolines.

Reversible Switching between Destructive and Constructive Quantum Interference Using Atomically Precise Chemical Gating of Single-Molecule Junctions.

Quantum interference (QI) plays an imperative role in the operation of molecular devices within the phase-coherent length, and it is vital to harness the patterns of QI, i.e., constructive and destructive interference. However, the size of the single-molecule device is too small compared to most gate electrodes. Those gates act like a backgate to affect the molecular component uniformly. Switching the patterns of QI in the same molecular skeleton remains challenging. Here, we develop the atomically precise gating strategy that manipulates the frontier orbitals of molecular components, achieving the complete switching of QI patterns between destructive to constructive QI and leading to a significant conductance modulation at room temperature. The chemical gating effect is exerted locally on the pyridine nitrogen through the selective interaction to cationic reagents, with which we can also control the switching reversibility as desired. We demonstrate the unique effect of atomically precise gating to modulate the quantum interference at the single-molecule scale, opening an avenue to develop new-conceptual electronic devices.

Releasing Antiaromaticity in Metal-Bridgehead Naphthalene.

As a fundamental chemical property, aromaticity guides the synthesis of novel structures and materials. Replacing the carbon moieties of aromatic hydrocarbons with transition metal fragments is a promising strategy to synthesize intriguing organometallic counterparts with a similar aromaticity to their organic parents. However, since antiaromaticity will endow compound instability, it is a great challenge to obtain an antiaromatic organometallic counterpart based on such transition metal replacement in aromatic hydrocarbons. Here, we report an efficient aromaticity transformation on aromatic naphthalene through the bridgehead replacement of an osmium fragment, leading to the unprecedented synthesis of metal-bridgehead naphthalene featuring a highly twisted structure as confirmed by X-ray crystallography characterization. Such a twisted conformation works together with its phosphonium substituents to release the antiaromaticity in the planar conformation of the metal-bridgehead naphthalene. Our findings prove the bridgehead involvement of transition metals in unexpected aromaticity modifications and open an avenue for novel metal-bridgehead complexes.

Tuning an Electrode Work Function Using Organometallic Complexes in Inverted Perovskite Solar Cells.

Low-work-function (WF) metals (including silver (Ag), aluminum (Al), and copper (Cu)) used as external cathodes in inverted perovskite solar cells (PSCs) encounter oxidation caused by air exposure and halogen-diffusion-induced corrosion, which threaten the long-term stability of the device. The cathode interlayer (CIL) has shown promise in reducing the metal WF and thus boosting the device power conversion efficiency (PCE). However, it remains a challenge for current CIL materials to enable high-WF metals (e.g., Au) to be used as cathodes to achieve PSCs with a superior PCE and long-term stability. Here, we use a series of synthesized (carbolong-derived) organometallic complexes as CILs to tune the electrode WF in inverted PSCs. Density functional theory calculations and surface characterizations show that the organometallic complexes that contain anions and cations are prone to form anion-cation dipoles on the metal surface, hence drastically reducing the metal's WF. Photovoltaic devices based on a Ag cathode, which was modified with these organometallic complexes, received a boosted PCE up to 21.29% and a remarkable fill factor that reached 83.52%, which are attributed to the dipole-enhanced carrier transport. The environmental stability of PSCs was further improved after employing Au as a cathode with these organometallic complexes, and the modified devices exhibited no efficiency loss after 4080 h storage measurements.

Association between Vitamin D and Risk of Stroke: A PRISMA-Compliant Systematic Review and Meta-Analysis.

BACKGROUND: Previous studies have shown inconsistent results for associations between vitamin D and risk of stroke. We gathered the existing published articles and conducted this meta-analysis with the aim to explore the association between vitamin D and risk of stroke. METHODS: We searched for articles exploring the association between vitamin D and risk of stroke and published before April 2021 in the following databases: PubMed, Web of Science, MEDLINE, EMBASE, and Google Scholar. All statistical analyses were made using STATA 12.0 software. Q test and I2 were applied to examine heterogeneities between studies. RESULTS: For the association between serum levels of 25(OH) vitamin D and risks of stroke, the present analysis included 20 cohort studies (including 213,276 participants) and a case-control analysis (including 13,642 participants). Additionally, the analysis included 15 studies (including 41,146 participants given vitamin D supplementation and 41,163 participants given placebo) to evaluate the influence of vitamin D supplementation on risk of stroke. Higher circulating levels of 25(OH) vitamin D were associated with a reduced risk of stroke (odds ratio/relative risk = 0.78, 95% confidence interval [CI]: 0.70-0.86, I2 = 41.5%, p = 0.025). However, the present analysis showed that vitamin D supplementation did not influence the risk of stroke (hazard ratio = 1.05, 95% CI: 0.96-1.14, I2 = 2.3%, p = 0.425). CONCLUSIONS: Our analysis indicated that lower circulating level of vitamin D was associated with an elevated risk of stroke, but extra supplement of vitamin D failed to show benefit in decreasing the risk of stroke. Further research and study are also needed to show the role of vitamin D in relation to stroke.

Influence of Er3+ concentration and Ln3+ on the Judd-Ofelt parameters in LnOCl (Ln = Y, La, Gd) phosphors.

The optical transition properties of trivalent rare earth (RE3+) doped luminescent materials have received extensive attention. The Judd-Ofelt theory is an effective tool for exploring the optical transition properties for the 4f-4f transitions of lanthanides. The aim of this work is to discover the effect of Er3+ concentration and different Ln3+ ions on the Judd-Ofelt parameters in LnOCl:Er3+ (Ln = Y, La, Gd) phosphors. Oxychloride LnOCl:Er3+ (Ln = Y, La, Gd) phosphors were produced via a single displacement reaction technique. The Judd-Ofelt calculation procedure for RE3+ doped powders was modified and then adopted to obtain the Judd-Ofelt parameters of Er3+ in the studied phosphors. Meanwhile, a new route for examining the Judd-Ofelt calculation quality was proposed and used. It was found that the Er3+ doping concentration slightly affects the optical transition properties of Er3+ in YOCl and LaOCl, but greatly affects the optical transition properties in GdOCl. Moreover, it was also found that the optical transition properties of Er3+ depend also on Ln3+ (Ln = Y, La, Gd) though the crystal structure of these compounds is similar. The Judd-Ofelt parameters of Er3+ are the smallest in LaOCl:Er3+, medium in YOCl:Er3+, but the biggest in GdOCl:Er3+ when the doping concentration is the same.

GABA releases from parvalbumin-expressing and unspecific GABAergic neurons onto CA1 pyramidal cells are differentially modulated by presynaptic GABAB receptors in mouse hippocampus.

Hippocampus CA1 pyramidal cells receive γ-aminobutyric acid (GABA) release from multiple GABAergic interneurons. Combining optogenetic strategy and whole-cell recordings, we demonstrate that baclofen, a specific GABAB receptor agonist, depresses monosynaptic GABAA receptor-mediated transmission from parvalbumin (PV)-expressing interneuron terminals onto pyramidal cells with less efficacy than that from the unspecific GABAergic terminals. The depression from PV neuron terminals is mainly mediated by presynaptic P/N type calcium channels. The results suggest that GABAB receptors are widely expressed on GABAergic interneurons, where they exert inhibition onto pyramidal cells by GABA release with different efficacy. The data strengthen the proposal that diverse GABA neurons play different roles in modulating CA1 pyramidal cell excitability.

Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals.

The construction of metal-carbon bonds is one of the most important issues of organometallic chemistry. However, the chelation of polydentate ligands to a metal via several metal-carbon bonds is rare. Metallapentalyne, which can be viewed as a 7-carbon (7C) chain coordinated to a metal via three metal-carbon bonds, was first reported in 2013. Although metallapentalyne contains a metal-carbon triple bond in a five-membered ring (5MR) and the bond angle around the carbyne carbon is only 129.5°, metallapentalyne exhibits excellent stability to air, moisture, and heat. Metallapentalyne possesses the rare planar Möbius aromaticity, which is in sharp contrast to the Hückel antiaromaticity in pentalyne. The metal fragment not only relieves the large ring strain present in pentalyne but also results in the transformation of the antiaromaticity in pentalyne to aromaticity in metallapentalyne. With the extension of the carbon chain from 7 to 12 carbon atoms, a series of novel polycyclic frameworks were constructed via the formation of several metal-carbon bonds. Some interesting phenomena were observed for these complexes. For instance, (1) the carbyne carbon of the 7C framework could react with both nucleophilic and electrophilic reagents, leading to the formation of 16- and 18-electron metallapentalenes; (2) σ aromaticity was first observed in an unsaturated system in the 8C framework; (3) two classical antiaromatic frameworks, cyclobutadiene and pentalene, were simultaneously stabilized in the 9C framework for the first time; (4) three fused 5MRs bridged by a metal are coplanar in the 10C framework; (5) the first [2 + 2 + 2] cycloaddition of a late transition metal carbyne complex with alkynes was realized during the construction of an 11C framework; (6) the largest number of carbon atoms coordinated to a metal atom in the equatorial plane was observed in the 12C framework; and (7) sharing of the transition metal by multiple aromatic units has seldom been observed in the metalla-aromatics. Therefore, the term carbolong chemistry has been used to describe the chemistry of these novel frameworks. More interestingly, carbolong complexes exhibit diverse properties, which could lead to potential future applications. As the discovery and creation of molecular fragments lead to advancements in chemistry, medical science, and materials chemistry, these novel polydentate carbon chain chelates might have important influences in these fields due to their facile synthesis, high stability, and unique properties.

Access to Metal-Bridged Osmathiazine Derivatives by a Formal [4+2] Cyclization.

Treatment of osmacyclopentadiene derivatives 1 with phenyl or isopropyl isothiocyanate gave the fused five and six-membered osmacycles 2-5 by a formal [4+2] cyclization. The facile protonation of the newly generated exocyclic imine in complexes 2-5 afforded conjugation-extended osmacycle derivatives 6-9. Compounds 2-9 each contain two main-group heteroatoms (N and S) in the fused six-membered ring located at the ortho (for S) and para (for N) positions relative to the osmium centre; these species can be regarded as rare osma-1,3-thiazine derivatives and represent the first fused metallathiazine derivatives. In contrast to the non-planar organic 6H-1,3-thiazine, nearly coplanar metallathiazines 8 and 9 can be achieved by tuning the groups on the two nitrogen atoms. These unique metal-bridged osma-1,3-thiazine derivatives exhibit remarkable stabilities, broad spectral absorptions spanning the visible spectra, and considerable photothermal properties, which suggests their potential applications in material science.