The cavities of artificial receptors are defined by how their components fit together. encapsulation specific molecules can thus be engineered considering geometric principles; however, intermolecular interactions and steric scale with receptor size, such that the ability to bind multiple guests from a class compounds remains current challenge. By employing metal-organic self-assembly, we have prepared triangular prism two different ligands is capable binding more than 20 natural products,...

ConspectusStructural DNA nanotechnology offers a unique self-assembly toolbox to construct soft materials of arbitrary complexity, through bottom-up approaches including origami, brick, wireframe, and tile-based assemblies. This can be expanded by incorporating interactions orthogonal base-pairing such as metal coordination, small molecule hydrogen bonding, π-stacking, fluorophilic interactions, or the hydrophobic effect. These allow for hierarchical long-range organization in supramolecular...

Abstract Pseudo‐octahedral M II 6 L 4 capsules result from the subcomponent self‐assembly of 2‐formylphenanthroline, threefold‐symmetric triamines, and octahedral metal ions. Whereas neutral tetrahedral guests most anions investigated were observed to bind within central cavity, tetraphenylborate bound on outside, with one phenyl ring pointing into cavity. This binding configuration is promoted by complementary arrangement rings intercalated guest between phenanthroline units host. The...

A porphyrin-edged metal-organic tetrahedron forms host-guest complexes containing 1-4 equiv of fullerene C60, depending on the solvent employed. The molecules C60 were bound anticooperatively within well-defined pockets; an X-ray crystal structure three fullerenes inside was obtained. Electrochemical measurements revealed that electron-accepting properties capsules altered mode encapsulation. binding multiple observed to increase electron affinity overall cluster, providing a noncovalent...

Abstract The design of aqueous probes and binders for complex, biologically relevant anions presents a key challenge in supramolecular chemistry. Herein, tetrahedral assembly with cationic faces corners is reported that capable discriminating between anionic neutral guests water. Electrostatic repulsion subcomponents can be overcome by the addition an template, or generating robust covalent framework incorporating tris(2‐aminoethyl)amine (TREN). resultant TREN‐capped, water‐soluble,...

Many useful principles of self-assembly have been elucidated through studies systems where multiple components combine to create a single structure. More complex systems, product structures self-assemble in parallel from shared set precursors, are also great interest, as biological exhibit this behavior. The greater complexity such leads an increased likelihood that discrete species will not be formed, however. Here we show how the kinetics govern formation metal–organic architectures...

We present a method for the directed self-assembly of interlocked structures and coordination complexes in set metal–organic hosts. New homo- heteroleptic metal complexes—species that cannot be prepared outside—form within cavities cuboctahedral cages. When linear bidentate guests macrocycles are sequentially introduced to host, rotaxane is threaded internally; resulting ternary host–guest complex new kind molecular gyroscope. Tetradentate segregate these cages into distinct spaces,...

The self-assembly of block copolymers is often rationalized by structure and microphase separation; pathways that diverge from this parameter space may provide new mechanisms polymer assembly. Here, we show the sequence length single-stranded DNA directly influence sequence-defined copolymers. While increasing led to predictable changes in self-assembly, changing only produced three distinct structures: spherical micelles (spherical nucleic acids, SNAs) flexible poly(thymine) DNA, fibers...

Here we regulate the formation of dissipative assemblies built from DNA using a merocyanine photoacid that responds to visible light. The operation our system and relative distribution species within it are controlled by irradiation time, initial pH value, concentration small-molecule binder inhibits reaction cycle. This approach is modular, does not require modification, can be used for several sequences lengths. Our design allows waste-free control nanotechnology, toward generation...

Abstract Biopolymers such as nucleic acids and proteins exhibit dynamic backbone folding, wherein site-specific intramolecular interactions determine overall structure. Proteins then hierarchically assemble into supramolecular polymers microtubules, that are robust yet dynamic, constantly growing or shortening to adjust cellular needs. The combination of energy-driven folding growth with structural stiffness length control is difficult achieve in synthetic polymer self-assembly. Here we show...

Zinc(II), a dimolybdenum(II) paddlewheel tetramine A, and 2-formylpyridine self-assembled to generate cubic ZnII8(LA)6 assembly. The faces of this assembly exhibited two distinct conformations, whereas the analogous FeII8(LA)6 framework displayed no such perturbation its structure. This variation in behavior is attributed subtle difference ligand rotational freedom between ZnII- FeII-cornered cubes. incorporation fluorinated MoII2 paddlewheel, B, into ZnII8(LB)6 FeII8(LB)6 structures...

Herein we elucidate the interplay of chiral, chelate, solvent, and hydrogen–bonding information in self-assembly a series new three-dimensional metal–organic architectures. Enantiopure ligands, each containing H-bond donors acceptors, form different structures, depending on ratio which they are combined: enantiopure components M4L4 assemblies, whereas racemic mixtures M3L3 stacks. Chiral amplification within enantiomers was observed when 2:1 R S subcomponent employed. Simply switching...

Biological systems employ multimetallic assemblies to achieve a range of functions. Here we demonstrate the preparation metal-organic cages that contain either homobimetallic or heterobimetallic vertices. These vertices are constructed using 2-formyl-6-diphenylphosphinopyridine, which forms ligands readily bridge between pair metal centers, thus enforcing formation bimetallic coordination motifs. Two pseudo-octahedral homometallic M

Abstract Hierarchical DNA nanostructures offer programmable functions at scale, but making these structures dynamic, while keeping individual components intact, is challenging. Here we show that the A‐motif—protonated, self‐complementary poly(adenine) sequences—can propagate origami into one‐dimensional, micron‐length fibrils. When coupled to a small molecule pH regulator, visible light can activate hierarchical assembly of our dissipative This system recyclable and does not require...

A ligand containing the thiazolo[5,4-d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N'-(thiazolo[5,4-d]thiazole-2,5-diylbis(4,1-phenylene))bis(N-(pyridine-4-yl)pyridin-4-amine (1), was designed as a donor-acceptor system for incorporation into electronically active metal-organic frameworks (MOFs). The capacity to undergo multiple sequential oxidation and reduction processes examined using UV/Vis-near-infrared spectroelectrochemistry (UV/Vis-NIR SEC) in...

Abstract Self‐assembled materials can be designed to express useful optoelectronic properties; however, achieving structural control is a necessary precondition for the optimization of desired properties. Here we report simple, metal‐templated polymerization process that generates helical metallopolymer strands over 75 repeat units long (28 kDa) from single bifunctional monomer and Cu I . The resulting polymer consists double helix two identical conjugated organic enclosing central column...

Molecules often mix in unexpected ways – we present a new method of calculating product distributions complex sorting systems.

Abstract Although a multitude of studies have explored the coordination chemistry classical tripodal ligands containing range main‐group bridgehead atoms or groups, it is not clear how periodic trends affect ligand character and reactivity within single family. A case in point extensive family neutral tris‐2‐pyridyl E(2‐py) 3 (E=C−R, N, P), which are closely related to archetypal tris‐pyrazolyl borates. With 6‐methyl substituted E(6‐Me‐2‐py) (E=As, Sb, Bi) hand, effects modification alone on...

Abstract Pseudo‐octahedral M II 6 L 4 capsules result from the subcomponent self‐assembly of 2‐formylphenanthroline, threefold‐symmetric triamines, and octahedral metal ions. Whereas neutral tetrahedral guests most anions investigated were observed to bind within central cavity, tetraphenylborate bound on outside, with one phenyl ring pointing into cavity. This binding configuration is promoted by complementary arrangement rings intercalated guest between phenanthroline units host. The...