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We report an unprecedented heterometallic aluminum oxo cluster (AlOC) containing four surface-exposed CoII sites, designated as Al12Co4, protected by four t-butylcalix[4]arene (TBC[4]) molecules. The Al12Co4 nanocluster represents a significant advancement on multiple innovative fronts. First, it stands as an pioneering example of an AlIII-based metallocalixarene nanocluster. It is also the first instance of heterometallic AlOCs shielded by macrocyclic ligands. Notably, this cluster also holds the distinction of being the highest nuclearity Al–Co bimetallic nanocluster known to date. Additionally, by depositing Al12Co4 on carbon nanotubes (CNTs) as a supported catalyst, we investigated its electrocatalytic performance for the oxygen evolution reaction in alkaline media. To reach a 10 mA cm−2 current density in alkaline solution, the Al12Co4@CNT electrode needs overpotential as low as 320 mV. [ABSTRACT FROM AUTHOR]

A large polymolybdate-templated {Ag49Mo16} cluster protected by six thiacalix[4]arene (TC4A) molecules was synthesized by a one-pot solvothermal reaction. Structural analysis shows that the {Ag49Mo16} is assembled by inserting a [Mo6O22]8− cluster into a [Ag49Mo10@(TC4A)6] cage, representing the first polyoxometalate-templated Ag cluster protected by calixarene macrocyclic ligands. The solution stability and photoelectric properties of {Ag49Mo16} are discussed. Furthermore, this POM-templated Ag nanocluster realized electrocatalytic CO2 reduction applications, and 44.75% CO faradaic efficiency (FE) was obtained at a voltage of −0.8 V (vs. RHE). [ABSTRACT FROM AUTHOR]

We report here the synthesis of a ferrocene-functionalized {Ti22Fc4} cluster with a 'dimer-of-clusters' topology, which represents the largest Ti-oxo cluster (TOC) modified with organometallic groups ever reported. The exact assembly path of {Ti22Fc4} can be inferred from its two substructures, {Ti11Fc2} and {Ti5Fc}, which can also be synthesized independently through subtle changes in reaction conditions. Furthermore, we used these clusters as photocatalysts, and have studied, for the first time, the photocatalytic activity of TOCs in the oxidative coupling of amines. [ABSTRACT FROM AUTHOR]

A novel metallo-organic ligand [RuL2] with four uncomplexed coordination sites was created, and upon treatment with Zn2+ generated a dimetallic 3D metallosupramolecule in nearly quantitative yield. This self-assembly process gave stable intermediates, opening the pathway to the first 3D metallo-assembly possessing two Ru2+, two Fe2+, and two Zn2+ ions precisely located in the different edges. This strategy opens the door to novel designer 3D polymetallic constructs capable of diverse applications. [ABSTRACT FROM AUTHOR]

A carbamoyl anion-initiated cascade reaction with acylsilanes and imines has been used to rapidly construct substituted α-hydroxy-β-amino amides. The Brook rearrangement-mediated cascade allows the formation of two C–C bonds and one O–Si bond in a single pot. Using this approach, a range of α-aryl α-hydroxy-β-amino amides has been synthesized in high yields with excellent diastereoselectivities. [ABSTRACT FROM AUTHOR]

Binding of the fluoride ion triggers aggregation of a pyreneboronic acid-catechol ensemble in acidic aqueous solutions, giving rise to intense excimer emission, allowing for sensitive fluoride ion sensing at ppm levels, with an apparent fluoride binding constant higher than 10³ M-1 which is unprecedented for boronic acid sensors in water. [ABSTRACT FROM AUTHOR]

A novel metallo-organic ligand [RuL2] with four uncomplexed coordination sites was created, and upon treatment with Zn2+ generated a dimetallic 3D metallosupramolecule in nearly quantitative yield. This self-assembly process gave stable intermediates, opening the pathway to the first 3D metallo-assembly possessing two Ru2+, two Fe2+, and two Zn2+ ions precisely located in the different edges. This strategy opens the door to novel designer 3D polymetallic constructs capable of diverse applications. [ABSTRACT FROM AUTHOR]