Coordination‐driven self‐assembly has led to the formation of various aesthetical polyhedrons and compounds with advanced functions. Whereas two‐dimensional supramolecules with complex and giant ...skeletons are plentiful, the constructions of polyhedrons are limited by using basic polygons as the panels. Herein, we report the modular synthesis of a tessellated triangle and tessellated octahedron with metal‐organic modules as the panels and formed via template‐driven self‐assembly. These architectures have diameters on the order of 10.9 nm and molecular weights greater than 84 kDa. Interestingly, fiber and spherical‐like nanostructures could be formed from the tessellated triangles and octahedrons, respectively, through hierarchical self‐assembly. In addition, after hybridization with carbon nanotubes, the supramolecules exhibit electrochemical reduction activity for CO2 to CO.
The self‐assembly of a tessellated triangle T1 and the construction of a tessellated octahedron O1 containing metal‐organic modules as the panels are demonstrated. O1 has a diameter on the order of 10.9 nm and a molecular weight greater than 84 kDa. After hybridization with carbon nanotubes, the supramolecules exhibit electrochemical reduction activity for CO2 to CO.
Coordination-driven self-assembly is a powerful approach for the construction of metallosupramolecules, but designing coordination moieties that can drive the self-assembly with high selectivity and ...specificity remains a challenge. Here we report two ortho-modified terpyridine ligands that form head-to-tail coordination complexes with Zn(II). Both complexes show narcissistic self-sorting behaviour. In addition, starting from these ligands, we obtain two sterically congested multitopic ligands and use them to construct more complex metallo-supramolecules hexagons. Because of the non-coaxial structural restrictions in the rotation of terpyridine moieties, these hexagonal macrocycles can hierarchically self-assemble into giant cyclic nanostructures via edge-to-edge stacking, rather than face-to-face stacking. Our design of dissymmetrical coordination moieties from congested coordination pairs show remarkable self-assembly selectivity and specificity.
The design principle of supramolecular architectures through a bottom-up strategy has always been guided by polyhedra such as Platonic solids, Archimedean solids, and prisms (antiprisms) with high ...symmetry. Non-uniform convex polyhedra with regular faces, i.e., Johnson solids, are rarely constructed experimentally although their topologies have been predicted through mathematical theory. Herein, self-assembly of a giant triangular orthobicupola Zn24612, one of 92 Johnson solids J27, has been achieved from the coordination between 24 Zn2+ and 12 tetrakis-terpyridine building blocks 6 in DMF (N,N-Dimethylformamide). Different from classical Oh or Td symmetric cuboctahedron, the structure of this triangular orthobicupola revealed D3 symmetry which has been unambiguously determined by synchrotron X-ray analysis, NMR, and mass spectrometry. Surprisingly, the self-assembly process has been found to be solvent dependent. The same Zn2+ and tetrakis-terpyridine ligand 6 assembled into another pentagonal prism with the composition of Zn20610 when using methanol as the reaction solvent.
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•Self-assembly of a Johnson solid J27: triangular orthobicupola with 5.2 nm diameter•Atomic resolution synchrotron X-ray crystallographic analysis of Zn24L12•Kinetic trapped product of triangular orthobicupola ruling out the cuboctahedron•Solvent-dependent supramolecular conversion to pentagonal prism Zn20L10 in MeOH
Although numerous metalla-supramolecules have been constructed with the realm of Platonic solids, Archimedean solids, and prisms (antiprisms), it remains a formidable challenge to assemble non-uniform convex polyhedra with regular faces, i.e., Johnson solids. In this contribution, a triangular orthobicupola with 5.2 nm in diameter, a characteristic Johnson solid J27, has been achieved through precise coordination-driven self-assembly of a polyterpyridine ligand. Synchrotron X-ray analysis has unequivocally confirmed its D3 symmetry, which is in conformity with a characteristic triangular orthobicupola geometry. In contrast to a highly symmetric cuboctahedron, the triangular orthobicupola reveals greatly increased complexity and less symmetry with a great step forward anfractuous self-assembly occurring in nature. In addition, solvent-dependent supramolecular conversion can be envisioned as an efficient approach to dynamic catching and releasing of guest molecules.
A highly symmetrical Archimedean solid cuboctahedron has been well reported, while its structural isomer triangular orthobicupola, a characteristic Johnson solid J27, has been rarely explored. Herein, we report a gigantic cage Zn24L12 with 5.2 nm diameter based on metal-terpyridine coordination-driven precise self-assembly in DMF. Synchrotron X-ray crystallographic analysis unambiguously confirmed its triangular orthobicupola geometry with reduced D3 symmetry. In addition, a very interesting solvent-triggered supramolecular conversion has been achieved.
Coordination‐driven self‐assembly has led to the formation of various aesthetical polyhedrons and compounds with advanced functions. Whereas two‐dimensional supramolecules with complex and giant ...skeletons are plentiful, the constructions of polyhedrons are limited by using basic polygons as the panels. Herein, we report the modular synthesis of a tessellated triangle and tessellated octahedron with metal‐organic modules as the panels and formed via template‐driven self‐assembly. These architectures have diameters on the order of 10.9 nm and molecular weights greater than 84 kDa. Interestingly, fiber and spherical‐like nanostructures could be formed from the tessellated triangles and octahedrons, respectively, through hierarchical self‐assembly. In addition, after hybridization with carbon nanotubes, the supramolecules exhibit electrochemical reduction activity for CO2 to CO.
The self‐assembly of a tessellated triangle T1 and the construction of a tessellated octahedron O1 containing metal‐organic modules as the panels are demonstrated. O1 has a diameter on the order of 10.9 nm and a molecular weight greater than 84 kDa. After hybridization with carbon nanotubes, the supramolecules exhibit electrochemical reduction activity for CO2 to CO.
The ability to construct complex molecular architectures with precise control is critical for realizing molecule‐based materials and functions. Using the assembly of a 60‐metal complex of ErIII with ...histidine as an example, we demonstrate the rational assembly of otherwise synthetically elusive polynuclear lanthanide hydroxide clusters directed by the combined set of I− and CO32− as templates. We succeeded in the stepwise transformation starting from Er12 to Er60 by way of two key intermediates Er34 and Er48. The Er12, Er34, and Er48 core motifs represent respectively 1/6, 1/2, and 3/4 of the complete sodalite cage of Er60. This work, representing a rare example of rationally constructing high‐nuclearity lanthanide clusters guided by judiciously chosen templates, is expected to stimulate more future efforts for the controllable synthesis of complex molecular or supramolecular architectures with unprecedented structural sophistication and possibly useful properties.
Deliberately introduced anions guide the hierarchical assembly of the series of high‐nuclearity lanthanide hydroxide cluster intermediates Er12, Er34, and Er48 toward the complete sodalite cage of Er60.
In the past decades, many supramolecular cages with different sizes and shapes have been achieved through coordination-driven self-assembly. However, the strategy of topology adjustment by using a ...steric hindrance effect has not been fully developed. In this Article, we report the synthesis of ligand LA with rotatable arms, ligand LB with restricted arms, and their precisely controlled self-assembly to tetramer cage T1 and dimer cage D1, respectively, under the same conditions. By utilizing the steric hindrance of the ligands, the shapes and sizes of metallosupramolecular cages have been successfully adjusted. The metallocages were characterized by NMR spectroscopy (1H, 13C, COSY, NOESY, and DOSY), mass spectrometry (ESI-MS, TWIM-MS), transmission electron microscopy, and atomic force microscopy. This synthetic method would have the potential to be a general strategy for the design and self-assembly of diverse cages with tunable shape, size, and applicable properties.
The rational synthesis of high‐nuclearity lanthanide clusters remains challenging. In their Research Article (e202205385), Min Feng, Zhiping Zheng, and co‐workers developed a stepwise synthesis of a ...high‐nuclearity sodalite cage‐like cluster Er60, guided by judiciously selected anions. The successive introduction of I−, CO32−, and NO3− led to the isolation of three crucial intermediate clusters, namely the wheel‐like Er12, ship‐like Er34, and bowl‐like Er48. These findings opened the “black box” of the elusive self‐assembly process and provided mechanistic insights.
Abstract
Coordination‐driven self‐assembly has led to the formation of various aesthetical polyhedrons and compounds with advanced functions. Whereas two‐dimensional supramolecules with complex and ...giant skeletons are plentiful, the constructions of polyhedrons are limited by using basic polygons as the panels. Herein, we report the modular synthesis of a tessellated triangle and tessellated octahedron with metal‐organic modules as the panels and formed via template‐driven self‐assembly. These architectures have diameters on the order of 10.9 nm and molecular weights greater than 84 kDa. Interestingly, fiber and spherical‐like nanostructures could be formed from the tessellated triangles and octahedrons, respectively, through hierarchical self‐assembly. In addition, after hybridization with carbon nanotubes, the supramolecules exhibit electrochemical reduction activity for CO
2
to CO.
The template-directed strategy has been extensively employed for the construction of supramolecular architectures. However, with the increase in the size and complexity of these structures, the ...synthesis difficulty of the templates escalates exponentially, thereby impeding the widespread application of this strategy. In this study, two truncated triangles T 1 and T 2 were successfully self-assembled through a novel segmented template strategy by segmenting the core triangular template into portions. Two metallo-organic ligands L 2 and L 3 were designed and synthesized by dividing the central stable triangle into three separate parts and incorporating them into the precursor ligands, which served as templates to guide the self-assembly process with ligands L 1 and L 4 , respectively. The assembled structures were unambiguously characterized by multidimensional and multinuclear NMR (1H, COSY, NOESY), multidimensional mass spectrometry analysis (ESI-MS and TWIM-MS), and transmission electron microscopy (TEM). Moreover, we observed the formation of fiberlike nanotubes from single-molecule triangles by hierarchical self-assembly.
In coordination-driven metal–organic cages, the transition metal ions are generally utilized as linkages. Employment of its unique properties with the aim of achieving specific applications still ...presents great challenges. Herein, we report a decametric metal–organic cage named pentagonal prism (Mn 20 LC 10 ) based on Tpy-Mn(II)-Tpy connectivity (Tpy = 2,2′:6′,2″-terpyridine) in which Mn(II) serves as a linker and endows the resulting metal–organic cage with good photosensitivity. In the photooxidation of benzaldehyde, pentagonal prism Mn 20 LC 10 showed a significantly increased level of 1O2 production, the fastest conversion time, good recyclability, and substrate versatility due to its greatly improved intersystem crossing ability. Notably, the abundant active sites of metal pentagonal prism Mn 20 LC 10 enable its photooxidation under solvent-free and daylight conditions. This work provides approaches for the development of inexpensive, green, and low-cost photosensitizer systems.
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