Organic–Inorganic High-Valence Sn₁₈-oxo Clusters: Direct Utilization of an Inorganic Sn(IV) Source to Improve the Nuclearity and Electrocatalytic CO₂ Reduction Properties

Abstract

The high-valence tin-oxo clusters are of great significance because of their structural diversity and potential applications in many fields, e.g., catalysis, extreme ultraviolet (EUV) lithography, and so on. The synthesis of high-nuclearity tin-oxo clusters remains a great challenge currently, since the key inorganic Sn x O y core with Sn 4+ ions could not be obtained only by the in situ Sn−C bond cleavage in organic tin sources. In this context, we synthesize three organic−inorganic hybrid Sn 18 -oxo clusters, [(BuSn) 12 Sn 6 (μ 3 -O) 20 (ba) 12 (PhPO 3 ) 4 ] (Bu = butyl, Hba = benzoic acid), [(BuSn) 12 Sn 6 (μ 3 -O) 20 (pmba, as well as one Sn 6 -oxo cluster [(BuSn) 6 (μ 3 -O) 2 (μ 2 -OH) 4 (pnba) 6 (PhPO 3 ) 2 ] (Sn 6 ) (Hpnba = p-nitrobenzoic acid) by combining an inorganic precursor (SnCl 4 ) with an organic one (butyltin hydroxide oxide). It is shown that an inorganic dicyclo-chain-like Sn 6 O 8 core encapsulated in a U-shaped dodecanuclear butyltin-oxo ring plays an important role in the construction of Sn 18 -oxo clusters and that the use of a ligand with an electron-withdrawing group reduces the nuclearity of clusters to Sn 6 . Moreover, electrocatalytic CO 2 reduction studies confirm that the electrocatalytic activities of the Sn 18 clusters are superior to those of the Sn 6 cluster, probably due to the hybrid organotin− inorganotin structures. Our work not only opens a new way for constructing high-nuclearity tin-oxo clusters but also is helpful in deeply revealing the structure−properties relationship of tin-oxo clusters.

Structures of Large Tin(IV) Oxo Clusters

“…This unit is wrapped by 12 BuSn units which are interconnected by the carboxylate and PhPO 3 ligands (in addition to oxygen bridges). [50]…”

“…The center of the clusters Bu 12 Sn 18 O 20 (OOCR) 12 (O 3 PPh) 4 (R=Ph, Tol, t BuC 6 H 4 ) is formed by six [SnO 6 ] octahedra. This unit is wrapped by 12 BuSn units which are interconnected by the carboxylate and PhPO 3 ligands (in addition to oxygen bridges) [50] …”

Ligand-controlled exposure of active sites on the Pd1Ag14 nanocluster surface to boost electrocatalytic CO2 reduction

“…25 In the realm of the electrocatalytic CO 2 reduction reaction (eCO 2 RR), a process gaining recognition for its potential in converting CO 2 into valuable chemicals sustainably, the application of metal nanoclusters is proving increasingly significant. [26][27][28][29] Research shows that alterations in the morphology, 30,31 structure, 32 active sites, 11,33 size, 34 ligand, 35 and alloying of metal nanoclusters can influence the eCO 2 RR outcomes. 36 A pertinent question arises: Can we manipulate and assess the effects of individual changes in surface ligands or metals on the catalytic selectivity for CO 2 electrocatalysis?…”

Lanthanum-Centered Organotin Oxysulfide Clusters with Substitutable Coordinating Amide Solvent Molecules for Tuning Blue Light Emission

“…Organometallic clusters have become a research hotspot because of their unique structural features and potential applications in many fields. − An important branch of them, organotin clusters, especially organotin-oxo or organotin-chalcogenide, has been widely used in optical light-emitting devices, extreme ultraviolet lithography, electrocatalysis, third-order nonlinear response materials, etc. − To date, many types of organotin-O clusters or organotin-S clusters have been reported, e.g., {( n BuSn) 22 Sn 4 O 48 }, {( n BuSn) 34 Na 2 O 54 }, {(PhSn) 4 S 6 }, {[(Me 3 P) 3 AuSn]­[(PhSn) 3 S 6 )]}, and {( n BuSn) 4 M 2 S 8 } (where n BuSn is n -butyltin). − The combination of ≥2 types of VIA-elements into the same organotin coordination system will not only enrich the cluster chemistry but also result in different functions associated with their electronic structures. − Nonetheless, organotin oxychalcogenide hybrid clusters have been less explored, due to the existence of coordination competition from O- and S/Se-atoms, making the realization of single O-based or S/Se-based clusters relatively easy and oxychalcogenide clusters, especially the heterometallic or organometallic oxychalcogenide clusters, extremely challenging.…”