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The construction of nanotubes with well-defined structures, although synthetically challenging, offers the prospect of studying novel chemical reactions and transportation within confined spaces, as well as fabricating molecular devices and nanoporous materials. Here we report a discrete molecular nanotube, namely the covalent organic pillar COP-1, synthesized through a [2 + 5] imine condensation reaction involving two penta-aldehyde macrocycles and five phenylenediamine linkers. A pair of enantiomeric nanotubes, obtained in a quantitative and diastereoselective manner, were characterized and resolved readily. NMR spectroscopy, isothermal titration calorimetric and X-ray crystallographic studies revealed that the 2-nm-long and 4.7-Å-wide one-dimensional channel inside COP-1 can accommodate α,ω-disubstituted n-alkyl chains with complementary lengths and electron density distributions. Furthermore, in a length-mismatched host–guest pair, we found that the nonamethylene dibromide thread not only displays a diminished binding constant in solution, but adapts an energetically unfavoured gauche conformation inside COP-1 in the solid state.

Coordination-driven self-assembly of metal ions and organic ligands has been extensively applied over the past few decades, towards construction of various functional two-dimensional (2D) and three...

Complementary complexation between 2,2&prime, 6&prime, 2&Prime, terpyridine (tpy) and 6,6&Prime, dianthracenyl-substituted tpy in the presence of Zn(II) ions provided an efficient strategy for construction of metallo-supramolecular diblock copolymers. To synthesize well-defined tpy-modified polystyrenes (PSs), an Fe(II) bis(tpy) complex bearing &alpha, bromoester as a metallo-initiator was applied to atom transfer radical polymerization (ATRP) to avoid poisoning the Cu(I) catalyst. Subsequently, a series of tpy-functionalized PSs was obtained after the decomplexation of &lt, tpy-Fe(II)-tpy&gt, junction by tetrakis(triethylammonium) ethylenediaminetetraacetate (TEA-EDTA) under mild conditions. The metallo-supramolecular poly(3-hexylthiophene) (P3HT)-block-PS diblock copolymers were prepared by simply mixing the corresponding terminally tpy-modified homopolymers with Zn(II) ions, and further characterized by 1H NMR and diffusion ordered spectroscopy (DOSY) experiments. The approach using metallo-initiators for ATRP offers an opportunity to construct tpy-functionalized polymers with controllable molecular weights and low polydispersities. Through the spontaneous heteroleptic complexation, a variety of metallo-supramolecular diblock copolymers with tunable block ratios can be easily constructed.

Supramolecular cages/vesicles in biology display sophisticated structures and functions by utilizing a few types of protein subunit quasi-equivalently at distinct geometrical locations. However, synthetic supramolecular cages still lack comparable complexity to reach the high levels of functionality found in natural systems. Herein we report the self-assembly of giant pentagonal supramolecular prisms (molecular weight >50 kDa) with tetratopic pyridinyl subunits serving different geometrical roles within the structures, and their packing into a novel superstructure with unexpected three-fold rotational symmetry in a single two-dimensional layer of crystalline state. The formation of these complicated structures is controlled by both the predetermined angles of the ligands and the mismatched structural tensions created from the multi-layered geometry of the building blocks. Such a self-assembly strategy is extensively used by viruses to increase the volume and complexity of capsids and would provide a new approach to construct highly sophisticated supramolecular architectures.

‘Aniono’ double helicates and grids were constructed using PO43– anions and a bis–tris(urea) ligand and interconverted by changing the counter-cation., Supramolecular assembly of well-defined discrete architectures has been of great interest due to the tunable properties of these structures in functional materials and bio-mimicking. While metal-coordination-driven assembly has been extensively studied, anion-coordination-driven assembly (ACDA) is just emerging for constructing complex supramolecular structures. Herein two A2nL2n (A = anion, L = ligand; n = 1 or 2) ‘aniono’-supramolecular assemblies, i.e. double helicates and the first anion grid, have been constructed based on the coordination between phosphate (PO43–) anion and a bis–tris(urea) ligand. Moreover, the aniono-grid and double helicate motifs can be readily interconverted under ambient conditions by simply changing the counter-cation. These results redefine the power and scope of ACDA, which may represent a new approach in the assembly of well-defined architectures in parallel with the metal coordination-driven assembly of metallo-supramolecules.

We present a series of tripodal ligands L1–3, which fold into hemicages C1–3 by using coordination-driven dynamic combinational chemistry. The identities of these hemicages were characterized using 1H NMR, 1H–1H COSY, DOSY, and ESI-TWIM-MS. Free rotation of the ferrocene structural units in the ligands affords an adaptable directionality, which is essential for the construction of these hemicages. Encapsulation of adamantane by C2 indicates the presence of a well-defined inner cavity as the binding pocket.

Metal-ligand coordination and host-guest recognition are introduced into the hybrid system in order to prepare supramolecular gels, which can be responsive to multiple external stimuli such as metal ions, competitive guest/host molecules, and oxidants. To this end, the triangular terpyridine-based metallocycles functionalized with 1-adamantyl and ferrocenyl groups are constructed through self-assembly, and further used as supramolecular cross-linkers for gelation of β-CD-containing copolymers. Their gelation and stimuli-response tests are discussed, and an application of the metallotriangles for serving as supramolecular glue is demonstrated through a series of adhesion experiments. This approach enables facile access to construction of multifunctional metallosupramolecules as well as functional hybrid materials.

How to orient polymers homeotropically in thin films has been a long-standing issue in polymer science because polymers intrinsically prefer to lie down. Here we provide a design principle for polymers that are processable into a 2D homeotropic order. The key to this achievement was a recognition that cylindrical polymers can be designed to possess oppositely directed local dipoles in their cross-section, which possibly force polymers to tightly connect bilaterally, affording a 2D rectangular assembly. With a physical assistance of the surface grooves on Teflon sheets that sandwich polymer samples, homeotropic ordering is likely nucleated and gradually propagates upon hot-pressing towards the interior of the film. Consequently, the 2D rectangular lattice is constructed such that its b axis (side chains) aligns along the surface grooves, while its c axis (polymer backbone) aligns homeotropically on a Teflon sheet. This finding paves the way to molecularly engineered 2D polymers with anomalous functions., Vertical alignment of polymers on surfaces is challenging due to their flexibility and tendency to arrange on horizontal planes. Here, the authors report a design principle allowing polymers to be arranged into 2D homeotropic orientations by using long-range dipole-dipole interactions and hot-pressing on Teflon sheets.

Femtosecond time-resolved absorption spectroscopy has been used to study the excited-state charge transfer dynamics in a set of self-assembled cyclic Fe(II)-bisterpyridine compounds with different π-conjugated ligands. By analyzing the dynamics, the internal conversion process involving a ligand-centered π-π* state to a lower lying metal-to-ligand charge transfer (MLCT) state was investigated. This is followed by intersystem crossing to the lowest MLCT state, which was found to occur at the ∼100 fs time scale. Vibrational cooling in the lowest MLCT state was found to occur on the 10s of femtoseconds time scale. The lowest MLCT state had an excited-state lifetime longer than 5 ns, indicating the possibility of light-induced excited-state spin trapping (LIESST).

Highly ordered mesoporous silicas with large accessible pores have been prepared by using pre-synthesized poly(ethylene oxide)- b -poly(methyl acrlyate) (EO n MA m ) diblock copolymers as templates. Via adjusting the chain length of EO versus that of MA, a series of silica mesostructures, including two-dimensional (2-D) hexagonal, 3-D bicontinuous ( Ia3d ), and body-centered cubic ( Im3m ) symmetries, were prepared with the use of tetraethyl-orthosilicate (TEOS) as the silica precursor under acidic conditions. The mesostructures of all materials were characterized by small-angle X-ray scattering and transmission electron microscopy measurements. N 2 adsorption–desorption isotherms reveal that the pore size ranges from 4 to 30 nm with a narrow pore-size distribution and its dimension is proportional to the chain length of MA units.

Poly(ethylene oxide)-b-poly(methyl acrylate) diblock copolymer (EOmMAn) prepared via an atom transfer radical polymerization (ATRP) approach was used as a template to synthesize Ia3d mesostructured silica with thick walls under acidic conditions.