Modification of Multi‐Component Building Blocks for Assembling Giant Chiral Lanthanide‐Titanium Molecular Rings

Abstract

Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi-component building block [Ln 3 Ti-(HSA) 6 (SA) 4 (H 2 O)] À ({Ln 3 Ti-SA}, H 2 SA = salicylic acid, Ln = Eu/Gd) to form new building blocks {Ln 3 Ti x -MSA} (H 2 MSA = 5-methoxysalicylic acid, x = 1, 2, 3) by constructing [Ti(MSA) 3 ] 2À units. The obtained {Ln 3 Ti x -MSA} can further assemble into a chiral Ln 22 Ti 14 ring with the formulae [Eu 22 Ti 14 (MSA) 48 (HMSA) 22 (CH 3 COO) 4 (H 2 O) 10 (iPrOH)] and [Gd 22 Ti 14 (MSA) 46 (HMSA) 26 (CH 3 COO) 4 (H 2 O) 8 ]. Parallel experiments without Ti 4 + result in linear Ln chains. Detailed analysis shows that the [Ti(MSA) 4 ] 4À unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA) 3 ] 2À further triggers interesting chiralsorting behavior. Finally, the electronic adsorption and magneto-optic responses of these molecular rings are investigated.

All-catecholate-stabilized black titanium-oxo clusters for efficient photothermal conversion

“…TOCs are oen grown as single crystals for precise structure determination, which is essential for establishing structure-property relationships at the molecular level. [16][17][18] While numerous TOCs with varying nuclearities and structures [19][20][21][22][23][24][25][26] have been discovered, including highnuclearity Ti 42 27 and Ti 52 , 28 many suffer from sensitivity to moisture due to the presence of alkoxy groups (-OR) derived from solvents or Ti(OR) 4 around their TiO cores. These alkoxy groups typically exhibit monodentate or bridging modes and offer insufficient protection.…”

Ligand Induced Double-Chair Conformation Ln12 Nanoclusters Showing Multifunctional Magnetic and Proton Conductive Properties

“…Lanthanide (Ln) clusters have always attracted wide attention due to their enchanting structures and interesting properties. In the past decades, people have reported many lanthanide clusters with different nuclear numbers. − Meanwhile, structures with various shapes and conformations are discovered, such as wheel, tube, disk, core–shell, and other atypical conformations. − This is very conducive for better understanding the cluster assembly mechanism and designing lanthanide clusters in the future. The construction of metal nanoclusters is usually affected by external factors during the preparation processes. − In general, to modulate structural conformations, one can screen the reaction conditions, for example, the ratio of metal and ligand, pH conditions, anion template, and so on. − However, these methods are often fussy.…”

Doping transition metals to modulate the chirality and photocatalytic activity of rare earth clusters

“…However, the construction of high-nuclear chiral rare earth clusters using achiral ligands is still limited. [17][18][19][20] In particular, metal center chirality can be canceled out by the opposite chirality of the assembled units, resulting in an mesomeric achiral cluster. 21 Due to the different coordination modes between transition metals and rare earth metals, the introduction of transition metals in the assembly process of high-nuclear rare earth cluster may be beneficial to regulate the chirality of individual metal centre within cluster, and then control the chirality of the entire cluster.…”