Sulfate and 1,10-phenanthroline ligands decorated Ti₁₇ and Ti₁₉-oxo clusters are prepared by ionothermal synthesis and show structure dependent photocatalytic MB dye degradation and photoelectrochemical photocurrent behaviors.

Comprehensive Summary

In this study, we successfully synthesized two titanium-oxo clusters, namely Ti₁₉(μ₃-O)₁₉(μ₂-O)₁₀(1,10-phn)₂(OⁱPr)₁₈] (PTC-178) and (EMIm)₃[Ti₁₇(μ₄-O)₄(μ₃-O)₁₆(μ₂-O)₄(SO₄)₃(μ₂-OⁱPr)₄(OⁱPr)₁₃] (PTC-179). These clusters were synthesized using an ionothermal reaction and possess similar nuclearity (Ti₁₉ vs. Ti₁₇) moieties. Additionally, we observed that these complexes exhibit varying activities for photocatalytic degradation of Methylene Blue (MB) dye and distinct photocurrent responses for photoelectrochemical studies due to their different surface-decorated ligands. This study provides valuable insights into the design of Ti-oxo molecular clusters with similar nuclearity but different surface environments, allowing for the establishment of critical structure-property relationships. Furthermore, our research contributes to the exploration of sustainable synthetic methods for high nuclearity TOCs using ionic liquids.

Here, we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity. Not only di- and tri-substituted hydrosilanes, but also alkoxysilane is suitable, which does explore the scope of the family of 1-amino-2-silyl compounds. The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time in this one-pot, two-step transformations.

Comprehensive Summary

Here, we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity. This difunctionalization reaction could undergo smoothly using 1 mol% catalyst loading with good functional group tolerance. Not only di- and tri-substituted hydrosilanes, but also alkoxysilane is suitable, which does explore the scope of the family of 1-amino-2-silyl compounds. The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time via absorption spectral analysis in this one-pot, two-step transformations. The primary mechanism has been proposed based on the control experiments.

Comprehensive Summary

Syringin is found in the root of Acanthopanax senticosus (Rupr. Maxim.) Harms and belongs to the lignin chemical compound with many biological activities. In this study, we employed commercially available starting materials and accomplished the total synthesis of syringin in 5 steps with an overall yield of 58%. Palladium-catalyzed C(O)–C bond activation and subsequent cross coupling reaction is the key to construct syringin and its natural analogues.

We report herein a palladium-catalyzed cyclizative alkynylation of allenyl ketones with terminal alkynes, which is proposed to follow a mechanism involving palladium-carbene migratory insertion.

Comprehensive Summary

Furans bearing alkynyl substituents are highly useful in organic synthesis. However, the methodologies to access these important furan derivatives are rather limited. We herein report an efficient synthesis of alkynylated furan derivatives based on Pd-catalyzed oxidative cross-coupling reaction between allenyl ketones and terminal alkynes. This novel synthesis of alkynylated furans with wide substrate scope is operationally simple and tolerates various functional groups. Mechanistically, the formation of the palladium carbene through cycloisomerization and the subsequent alkynyl migratory insertion are proposed as the key steps in the transformation. The reaction reported in this paper further demonstrates the generality of the carbene-based cross coupling.

A cross-coupling of aldehydes with α-haloboronates has been achieved under dual nickel/photoredox catalysis system. Considering the easy preparation of α-haloboronates with our deoxygenative difunctionalization of carbonyls (DODC) strategy, this protocol provides a formal deoxygenative cross-coupling of aldehydes to one-carbon-prolonged ketone products. The mild conditions enabled good functional group tolerance and broad substrate applicability. The application of this method was presented via a tunable synthesis of two ketones with very similar skeletons from two same aldehydes.

Comprehensive Summary

Aldehydes are a kind of important synthons and reagents in organic synthesis. The efforts on transformations of aldehydes are highly rewarding and have always attracted considerable attention. Herein, a cross-coupling of aldehydes with α-haloboronates has been achieved under dual nickel/photoredox catalysis system. Considering the α-haloboronates can be easily obtained from aldehydes with our deoxygenative difunctionalization of carbonyls (DODC) strategy, this protocol provides a formal deoxygenative cross-coupling of aldehydes to one-carbon-prolonged ketone products. The mild conditions enabled good functional group tolerance and broad substrate applicability. The application of this method was presented via a tunable synthesis of two ketones with very similar skeletons from two same aldehydes.

Comprehensive Summary

Tetralin-1-carboxamides are frequently incorporated in myriad medicinally important molecules. However, their existing synthetic routes not only suffer from some drawbacks such as tedious procedures, harsh reaction conditions, narrow substrate scope, low yields, and environmental problems, and are also based upon the elaboration of uneasily available non-linear tetralin derivatives. Herein we describe a metal- and additive-free visible light-induced [4+2] annulation of two simple linear starting materials, namely acrylamides and 2-benzyl-2-bromocarbonyls, through a cascade C(sp³)−Br/C(sp²)−H bond cleavage, double C−C bond formation, and aromatization sequence. The developed protocol provides a convenient, efficient, and green approach to a variety of tetralin-1-carboxamide derivatives with good functional group compatibility. Importantly, the resulting products could also undergo the LiCl-mediated mono-decarboxylative cyclization process to further furnish the architecturally novel bridged polycyclic imides with excellent cis-diastereoselectivities.

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Comprehensive Summary

Charge transport characterization of single-molecule junctions is essential for the fundamental research of single-molecule physical chemistry and the development towards single-molecule electronic devices and circuits. Among the single-molecule conductance characterization techniques, the single-molecule break junction technique is widely used in tens of worldwide research laboratories which can generate a large amount of experimental data from thousands of individual measurement cycles. However, data interpretation is a challenging task for researchers with different research backgrounds, and the different data analysis approaches sometimes lead to the misunderstanding of the measurement data and even reproducibility issues of the measurement. It is thus a necessity to develop a user-friendly all-in-one data analysis tool that automatizes the basic data analysis in a standard and widely accepted way. In this work, we present the XMe Code (Xiamen Molecular Electronics Code), an intelligent all-in-one data analysis tool for the comprehensive analysis of single-molecule break junction data. XMe code provides end-to-end data analysis that takes in the original experimental data and returns electronic characteristics and even charge transport mechanisms. We believe that XMe Code will promote the transparency of the data analysis in single-molecule electronics and the collaborations among scientists with different research backgrounds.

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Poly(3-hydroxyalkanoates) (PHA), promising biodegradable polymers, are hindered by the lack of efficient catalytic systems for competitive commercialization. Addressing this, we introduce a chloro-bridged dimeric salphen zirconium cobaltate complex. Under mild conditions under base-free conditions, it achieves full monomer conversion, 92% PHA selectivity, and challenges the prevailing β-lactone pathway. Instead, direct epoxide and carbon monoxide co-polymerization emerges as a unique and efficient PHA synthesis mechanism

Comprehensive Summary

Poly(3-hydroxyalkanoates) (PHAs) are a promising class of biodegradable polymers, exhibiting properties comparable to traditional petroleum-based counterparts. Nonetheless, the widespread commercialization of PHAs is hindered by the absence of an efficient and economically viable catalytic system, impeding their competitiveness against non-biodegradable polymers. In an effort to address this challenge, we present a study on a newly developed chloro-bridged dimeric salphen zirconium cobaltate complex for the direct synthesis of PHAs via carbonylative polymerization of epoxides. The catalytic system demonstrates favorable activity under mild reaction conditions, enabling complete monomer conversion and an impressive 92% selectivity towards PHA formation. Through meticulous control experiments and mechanistic studies, we have gained crucial insights into the polymerization process. Remarkably, our findings challenge the prevailing notion of sequential ring-opening polymerization of in-situ generated β-lactones as the primary pathway. Instead, we demonstrate that the polymerization predominantly proceeds through direct co-polymerization of epoxide and carbon monoxide, unveiling a unique and efficient mechanism for PHA synthesis.

S doping can promote H₂O activation and adjust Co active site. As a result, Co₁-SNC catalyst exhibits a greatly enhanced CO₂RR to CO performance compared to Co₁-NC.

Comprehensive Summary

Electrocatalytic reduction of CO₂ to fuels and chemicals possesses huge potential to alleviate current environmental crisis. Heteroatom doping in metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) has been found to be capable to promote the electrocatalytic CO₂ reduction reaction (CO₂RR). However, the origin of the enhanced activity is still elusive. Here, we report that sulfur-doped cobalt-nitrogen-carbon single-atom catalyst (Co₁-SNC) exhibits superior CO₂RR performance compared to sulfur-free counterpart (Co₁-NC). On the basis of in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), kinetic isotope effect (KIE) and theoretical calculation, it is demonstrated that sulfur doping can promote water activation, elevate the d-band center of Co active site, and reduce the free energy of *COOH intermediate formation. This work deepens the understanding of the CO₂RR chemistry over heteroatom-doped SACs for designing efficient CO₂RR processes.

The first asymmetric hydrogenation of tetrapyridine-type N-heteroarenes, catalyzed by phosphine-free chiral cationic ruthenium diamine complexes, was successfully developed. With this methodology, a broad range of enantiopure tetradentate pyridine-amine-type ligands were obtained in high yields (up to 93%) with excellent stereoselectivities (up to 92 : 8 dl/meso and >99% ee) under mild conditions. Furthermore, the resulting tetradentate nitrogen-donor ligands were successfully applied in the Cu-catalyzed asymmetric Friedel–Crafts alkylation of indoles.

Comprehensive Summary

Chiral ruthenium-catalyzed enantioselective hydrogenation of tetrapyridine-type N-heteroarenes was firstly developed. The partial reduction of adjacent tetraheteroaromatic substrates proceeded smoothly in the presence of phosphine-free chiral cationic ruthenium diamine complexes, affording unprecedented high reactivity, enantioselecitivity and diastereoselectivity (up to 93% yield, >99% ee and 92 : 8 dr). The potential application of chiral tetradentate pyridine-amine products as chiral ligands has been demonstrated in the Cu-catalyzed asymmetric Friedel–Crafts alkylation reaction between indoles and nitroalkenes.