Designable Aluminum Molecular Rings: Ring Expansion and Ligand Functionalization

Abstract

Presented herein are the AlIII molecular ring architectures from 8‐ring to 16‐ring. Although there are numerous reported cyclic coordination compounds based on transition metals, gallium, or lanthanides, the Al versions are less developed due to the fast hydrolysis nature of Al3+ ion. With the assistant of monohydric alcohols, a series of atomic precisely Al molecular rings based on benzoates are synthesized. The ring expansion of these Al‐rings from 8‐ring to 16‐ring is related to the monohydric alcohol structure‐directing agents. Moreover, the organic ligands on the Al‐rings can be modified by using various benzoate derivatives, which lead to tunable surface properties of the Al‐rings from hydrophilicity to ultra‐hydrophobicity. Importantly, 4‐aminobenzoic acid bridged 16‐ring is soluble in organic solvents and exhibits high solution stability revealed by mass spectroscopy. Ligand substitution also can be performed between these Al‐rings, which reveal controllable ligand functionalization of these Al‐rings.

Designable Al32‐Oxo Clusters with Hydrotalcite‐like Structures: Snapshots of Boundary Hydrolysis and Optical Limiting

“…Hence, a similar synthetic method can be adopted for the construction of AlOCs [11] . Very recently, a series of aluminum molecular rings were synthesized by using CDH strategy [12] . In this work, a typical synthesis of the Al 32 clusters involves mainly three‐component solvothermal reactions with high phase purity under the optimized reaction conditions (Supporting Information, Figures S1–S8).…”

“…[11] Very recently,aseries of aluminum molecular rings were synthesized by using CDH strategy. [12] In this work, at ypical synthesis of the Al 32 clusters involves mainly three-component solvothermal reactions with high phase purity under the optimized reaction conditions (Supporting Information, Figures S1-S8). Their structural components were confirmed by energy dispersive X-ray analysis (Figures S9-S15) and infrared spectroscopy (Figures S16-S22).…”

Designable Assembly of Aluminum Molecular Rings for Sequential Confinement of Iodine Molecules

“…Coordination-Driven Self-Assembly of Heterometallic Frameworks Thec olorless crystals of Al 10 (INA) 10 (OEt) 20 (Al 10 ) (INA = isonicotinate, AlOC-79,F igure 2a)r ings were isolated according to our general synthesis of aluminum molecular rings (Figure 2b and S1). [21] Initial management of obtaining such aluminum molecular rings with extra coordination anchors encouraged us to explore their further assembly behavior. When adding cuprous thiocyanate in the reaction system of AlOC-79,yellow crystals of AlOC-80 were isolated (Figure S2).…”

“…Thea ssembly strategy is applicable and attempts to construct architectures based on different ring sizes were successful (Figure S8). In the course of further assembly,t he variety of copper salts and the presence of methylamine ethanol solutions play an important role.When cupric nitrate trihydrate is employed and the dosage of the methylamine ethanol solution is increased from 40 mLi nAlOC-82 to 120 mL, architecture is the presence of mesoporous rdo cages.T he rhombic dodecahedron cage is composed of six chargeneutral Al 8 (IN) 12 (OH) 4 (OPr n ) 8 (Al 8 ,i sostructural to the reported discrete ring, [21] S12). Bond valence sum (BVS) analysis (Table S1) combined with the XPS results (Figure S13) showed that the valence state of Cu centers with tetrahedral and planar Cu geometry was + 1and + 2, respectively.Asaresult, the whole architecture of Al 3f).…”

Discovery and Supramolecular Interactions of Neutral Palladium‐Oxo Clusters Pd16and Pd24

“…Some neutral Ti IV and Zr IV ‐based oxo‐clusters with the general formula M x O y (OH) z (RCOO) n (M=Ti IV , Zr IV ) are known, wherein the metal‐oxo/hydroxo clusters are capped by monoanionic, bidentate carboxylate groups [3a–e] . Very recently, neutral Al III ‐oxo clusters have been reported with the general formula Al(OH) x (OR) y (R′OOCPh) 3− x − y [3f] . A similar strategy was employed recently to isolate a neutral Ru III ‐based oxo‐cluster [21] .…”