Metal–Helix Frameworks Formed by μ₃‐NO₃⁻ with Different Orientations and Connected to a Heterometallic Cu^II₁₀Dy^III₂ Folded Cluster

Abstract

Metal nanoclusters have a certain rigidity due to their specific coordination patterns and shapes; thus, they face extreme difficulty in folding into a specific direction to form a double‐helix structure and in further interconnecting to form metal–helix frameworks (MHFs). To date, no MHFs have been produced by the formation of heterometallic clusters. Selecting the appropriate “bonding molecules” to bond metal nanoclusters in a specific multiple direction is one of the most effective strategies for designing synthetic MHFs. In this study, we realized for the first time the control of different orientations of μ3‐NO3− to join heterometallic clusters (Cu10Dy2) and subsequently form a left‐handed double helix chain, which further joins to form MHFs. In the structure of the MHFs, four different directions of bridging μ3‐NO3− exist, three of which are involved in the linkage of the double‐helix chain. Each μ3‐NO3− is connected to three adjacent Cu10Dy2. Herein, we extend a new method for designing synthetic double‐helix structures and MHFs, thereby further laying the foundation for the development of similar DNA double‐helix structures and nucleic acid secondary structures in vitro.

Slow Magnetic Relaxation in a Co2Dy Trimer and a Co2Dy2 Tetramer

“…Adjacent to the phenolate O atom on one side there is a 1,2‐propanediolamine group and on the other side a methoxy group. This ligand has also been used by other groups to design promising homo and heterometallic 3d, 4f, 1s–3d and 1s–2p–3d complexes [27–33] . The coordination modes adopted by the ligand in complexes 1 and 2 are depicted in Figure S3 in the Supporting Information.…”

Temperature‐induced formation of two dinuclear dysprosium complexes with different magnetic properties

“…Designing and synthesizing complexes with beautiful structures and expanding their properties are the basic goals of coordination chemistry . The structure of an organic ligand usually does not change during the formation of a complex with a specific connection and topological structure via coordination among the organic ligand, coordinating anion and metal ion .…”

“…The structure of an organic ligand usually does not change during the formation of a complex with a specific connection and topological structure via coordination among the organic ligand, coordinating anion and metal ion . In recent years, hydrothermal/solvothermal technology has gradually become an important synthetic means, and a directional construction of new organic frameworks, coordination polymers and coordination molecular clusters has been achieved . Under solvothermal conditions, owing to the effects of temperature and pressure, certain metal ions with strong catalytic ability can further catalyze the reaction of the starting ligand by coordinating under in situ conditions, which will produce several organic compounds that are difficult to build via traditional organic synthesis .…”

“…While additional examples of organic ligands involved in coordination during the formation of complexes have been found, these examples are mostly involved in the formation of 3d metal complexes . Lanthanide metal ions have difficulty undergoing complex in situ ligand reactions during the formation of lanthanide complexes owing to their strong coordination ability, strong selectivity of coordination atoms, and complex and varied coordination configurations . Therefore, the expansion of in situ ligand tandem reactions catalyzed by lanthanide metal ions is crucial for the design, synthesis and performance regulation of lanthanide complexes.…”

Structure and Magnetic Properties of Two Discrete 3d‐4f Heterometallic Complexes

“…In addition, the suitable noncoordinating groups as a steric factor are also very important in achieving the adjustments of coordination geometries and topologies. [32][33][34] As well known, the ligand bearing coordination pockets can effectively bind to 3d and 4 f metal ions. A modification of such ligands with non-coordinating groups such as methyl is usually facile for reducing the dimensionalities to give discrete polynuclear complexes.…”