Hierarchical Assembly of High-Nuclearity Copper(I) Alkynide Nanoclusters: Highly Effective CO Electroreduction Catalyst toward Hydrocarbons.

The pursuit of precision in the engineering of metal nanoparticle assemblies has long fascinated scientists, but achieving atomic-level accuracy continues to pose a significant challenge. This research sheds light on the hierarchical assembly processes of two high-nuclearity Cu(I) nanoclusters (NCs). By employing a multiligand cooperative stabilization strategy, we have isolated a series of thiacalix[4]arene (TC4A)/alkynyl coprotected Cu(I) NCs (, where = , , , ).

Ag incorporation a Zr-anchored metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic clusters for enhanced eCORR-to-CO activity.

Attaining meticulous dominion over the binding milieu of catalytic metal sites remains an indispensable pursuit to tailor product selectivity and elevate catalytic activity. By harnessing the distinctive attributes of a Zr-anchored thiacalix[4]arene (TC4A) metalloligand, we have pioneered a methodology for incorporating catalytic Ag sites, resulting in the first Zr-Ag bimetallic cluster, ZrAg, which unveils a dualistic configuration embodying twin {ZrAg(TC4A)} substructures linked by an {AgSal} moiety. This cluster unveils a trinity of discrete Ag sites: a pair ensconced within {ZrAg(TC4A)} subunits and one located between two units.

Atomically Precise MoCu Bimetallic Nanocluster: Synergistic MoO-Coupled Copper Alkynyl Cluster for the Improved Hydrogen Evolution Reaction Performance.

Electrolytic hydrogen production via water splitting holds significant promise for the future of the energy revolution. The design of efficient and abundant catalysts, coupled with a comprehensive understanding of the hydrogen evolution reaction (HER) mechanism, is of paramount importance. In this study, we propose a strategy to craft an atomically precise cluster catalyst with superior HER performance by cocoupling a MoO structural unit and a Cu(I) alkynyl cluster into a structured framework.

Atomically accurate site-specific ligand tailoring of highly acid- and alkali-resistant Ti(iv)-based metallamacrocycle for enhanced CO photoreduction.

Skillfully engineering surface ligands at specific sites within robust clusters presents both a formidable challenge and a captivating opportunity. Herein we unveil an unprecedented titanium-oxo cluster: a calix[8]arene-stabilized metallamacrocycle (TiL), uniquely crafted through the fusion of four "core-shell" {Ti@(TBC[8])(L)} subunits with four oxalate moieties. Notably, this cluster showcases an exceptional level of chemical stability, retaining its crystalline integrity even when immersed in highly concentrated acid (1 M HNO) and alkali (20 M NaOH).

Stepwise assembly of thiacalix[4]arene-protected Ag/Ti bimetallic nanoclusters: accurate identification of catalytic Ag sites in CO electroreduction.

The accurate identification of catalytic sites in heterogeneous catalysts poses a significant challenge due to the intricate nature of controlling interfacial chemistry at the molecular level. In this study, we introduce a novel strategy to address this issue by utilizing a thiacalix[4]arene (TC4A)-protected Ti-oxo core as a template for loading Ag ions, leading to the successful synthesis of a unique Ag/Ti bimetallic nanocluster denoted as TiAg. This nanocluster exhibits multiple surface-exposed Ag sites and possesses a distinctive "core-shell" structure, consisting of a {Ti@Ag(TC4A)} core housing a {TiO@Ag(TC4A)} motif and two {Ti@Ag(TC4A)} motifs.

Atomically accurate structural tailoring of thiacalix[4]arene-protected copper(II)-based metallamacrocycles.

Accurate manipulation of ligands at specific sites in robust clusters is attractive but difficult, especially for those ligands that coordinate in intricate binding patterns. By linking the shuttlecock-like {Cu(μ-Cl)TC4A} motif and the phenylphosphate (PhPO) ligand, we elaborately design and synthesize two Cu(II)-thiacalix[4]arene metallamacrocycles (MMCs), namely CuL and CuL, which have regular triangular and quadrilateral topologies, respectively. While keeping the core intact, the Cl and PhPO in those two MMCs, which coordinated in a μ-bridging fashion, can be accurately substituted with salicylate ligands.