Finite, Spherical Coordination Networks that Self‐Organize from 36 Small Components

Abstract

Highly symmetric structures often appear in nature as revealed by, for example, the capsids of spherical viruses that have icosahedral symmetry consisting of 60n identical protein subunits.[1] The reason for the high symmetry lies behind the principle that increasing the number of elements with the same symmetry reduces the amount of independent structural information, which is directly related to the length of DNA. Thus, the self-organization of tiny subunits into a giant biological molecule can be regarded as the process of not only structural growth but of the amplification of molecular information. We show herein that, through metal-ligand interactions, [2,3] simple banana-shaped organic molecules self-organize into finite, spherical coordination networks with a diameter of up to 7 nm, which is in contrast to the formation of two-dimensional (2D) infinite networks that occurs with linear organic ligands. The spherical coordination networks consist of 36 components, 12 equivalent metal centers (M) and 24 equivalent ligands (L), and have cuboctahedron symmetry. By attaching a functional group (e.g., C 60 or porphyrin) to each ligand, 24 functional groups are aligned equivalently at the periphery of the sphere.Over the last decade, extensive studies have been made on infinite coordination networks that are formed by the complexation of exo-multidentate ligands with transitionmetal ions. A typical and simple example is given by a 2D grid complex that forms from a rodlike ligand and a metal (Figure 1 a). [4] We expect that, if the ligand framework is slightly bent, the coordination network will develop with a[*] Dr.

Bottom‐Up Construction of Mesoporous Nanotubes from 78‐Component Self‐Assembled Nanobarrels

“…When using [(bpy) 2 Pd 2 (NO 3 ) 2 ](3b;bpy = 2,2'-bipyridine) instead of 3a, 1 HNMR, DOSY,E SI-TOF-MS,a nd DLS spectroscopic data (Supporting Information,Figures S14,17,22,23,25) all confirmed the quantitative formation of barrellike discrete complex 4bin solution. However,itisinteresting to note that discrete barrel structure 4b is transformed into infinite MMONT 5 during the crystallization process ( Figure 3).…”

Supramolecular blueprint approach to metal-coordinated capsules

“…There are limited examples of large discrete multicomponent spheroid assemblies with large molecular cavities that contain functional groups on its periphery surface (14). Our elegant metal-directed self-assembly of 24 Cu(II) metal ions with 6 pyrogallol [4]arene macrocycles resulted in 24 hydroxyl groups attached at the nanocapsule periphery.…”

“…Nevertheless, for the construction of discrete assemblies with large molecular cavities, the molecular paneling approach by Fujita and coworkers (13) has received the most success. Indeed, an amazingly large discrete functionalized spherical coordination network assembled from 12 metal ions and 24 exo-multidentate ligands was recently reported (14). However, an inherent complication of using n-dimensional pyridine-like spacer multidentate ligands in coordination is the resultant high positive charge combined with porous surfaces within these supramolecular assemblies.…”

Oligo(p‐phenyleneethynylene)‐functionalized Perylenebisimidetriad: Synthesis, Photophysical Properties, and Self‐assembly

“…[19] In particular, nanopatterning has become one of the major topics in these fields. [20] The STM is a powerful tool to investigate two-dimensional organization of functionalized organic molecules at a solid-liquid interface, which provides access to molecular and supramolecular structure and dynamics on the single-molecule level. [21] For example, DeFeyter and De Schryver have reported two-dimensional self-assembly of D-A triads based on perylenebisimides and oligo(p-phenylenevinylene)s (OPV 4 -PDI-OPV 4 ) [22] at solid-liquid interface.…”