Assembly of Dy60 and Dy30 cage-shaped nanoclusters

Abstract

Rapid kinetics, complex and diverse reaction intermediates, and difficult screening make the study of assembly mechanisms of high-nuclearity lanthanide clusters challenging. Here, we synthesize a double-cage dysprosium cluster [Dy 60 (H 2 L 1 ) 24 (OAc) 71 (O) 5 (OH) 3 (H 2 O) 27 ]·6-H 2 O·6CH 3 OH·7CH 3 CN (Dy 60 ) by using a multidentate chelate-coordinated diacylhydrazone ligand. Two Dy 30 cages are included in the Dy 60 structure, which are connected via an OAc − moiety. The core of Dy 60 is composed of 8 triangular Dy 3 and 12-fold linear Dy 3 units. We further change the alkali added in the reaction system and successfully obtain a single cageshaped cluster [Dy 30 (H 2 L 1 ) 12 (OAc) 36 (OH) 4 (H 2 O) 12 ]·2OH·10H 2 O·12CH 3 OH·13CH 3 CN (Dy 30 ) with a perfect spherical cavity, which could be considered an intermediate in Dy 60 formation. Time-dependent, high-resolution electrospray ionization mass spectrometry (HRESI-MS) is used to track the formation of Dy 60 . A possible self-assembly mechanism is proposed. We track the formation of Dy 30 and the six intermediate fragments are screened.

Structural Chemistry of Giant Metal Based Supramolecules

“…China), demonstrates that supramolecules can be connected by means of bridging ligands into oligomers (Figure 56d,e). 327 Here, two smaller {Dy 30 } MOCs of 3.2 nm in ø each give rise to the dimeric MOC of as much as 5.7 nm in ø. Polymerization of MOCs is also possible. Although polymeric structures are beyond the scope of this review, interested readers are recommended to turn their attention toward section 3 in the recent review by El-Sayed and Yuan focusing this topic.…”

“…(a) Ligand L 3 ; (b, c) [Pd 30 (L 3 ) 60 ] 60+ and [Pd 48 (L 3 ) 96 ] 96+ ; and (d, e) H 2 L 5 and [Dy 60 (H 2 L 5 ) 24 (OAc) 71 O 5 (OH) 3 (H 2 O) 27 ]. H atoms on (b, c, and e) are omitted. , …”

A Series of High-Nuclear Gadolinium Cluster Aggregates with a Magnetocaloric Effect Constructed through Two-Component Manipulation

“…Designing and synthesizing high-nuclear lanthanide clusters with specific connections and functions have always been favored by coordination chemists. − To date, great progress has been made in the structural design and functional expansion of high-nuclear lanthanide clusters, particularly in molecular magnetism. − In general, the factors that must be considered for the structural design and functional modification of high-nuclear clusters primarily include ligands, metal ions, coordination solvent molecules, bridging ligands, and auxiliary ligands. ,,, Considering the diversified adjustable factors, coordination chemists often adopt the controlled variable method (the most commonly used physical and mathematical method) to control multiple variables and regulate a single factor. ,, Regulating a single variable greatly simplifies the complexity of the structural design. Although great progress has been made, simple single-variable regulation can no longer satisfy the rapidly developing cluster chemistry. , Therefore, developing and expanding the structural design of di/multivariate control for high-nuclear clusters are necessary.…”

Two Decanuclear DyIIIxCoII10–x (x = 2, 4) Nanoclusters: Structure, Assembly Mechanism, and Magnetic Properties

“…This is more obvious for high-nuclear 3d–4f clusters because 3d and 4f metal ions have significantly different coordination abilities and selectivities to ligands, which imposes difficulties in the design of ligands and complexity for the self-assembly of clusters (SMMs). , Therefore, it is very important to find a suitable method for exploring the assembly mechanism of heterometallic clusters by tracking their formation processes. High-resolution electrospray ionization mass spectrometry (HRESI-MS) has the advantages of high recognition, high sensitivity, less sample consumption, and real-time monitoring, − which was, therefore, widely used in recent years for mechanistic investigations of the formation of lanthanide clusters, heteropolyacids, coordination molecular cages, and 3d metal clusters. − However, only two 3d–4f clusters were reported using HRESI-MS in tracking their assembly mechanisms. In 2018, Zheng et al tracked the assembly process of a wheel-like cluster of Eu 24 Ti 8 using HRESI-MS .…”