Autotandem Catalyst: From Acylhydrazones to N',N'-Methylaliphatic Acylhydrazides via Transfer Hydrogenation/N-Methylation with Methanol Catalyzed by a Cp* Iridium Complex Bearing a Functional Ligand.

A new strategy for the synthesis of N',N'-methylaliphatic acylhydrazides from acylhydrazones via transfer hydrogenation/N-methylation with methanol as both the hydrogen source and the methylating reagent has been proposed and accomplished. In the presence of [Cp*Ir(2,2'-bpyO)(H2O)] (1 mol %) and Cs2CO3 (0.3 equiv), a range of desired products were obtained in high yields. It was also confirmed that functional units in the bpy ligand of the catalyst are crucial for the catalytic activity of iridium complexes. The mechanistic investigation and practical application of the present catalytic system were also presented.

Removing miscellaneous heavy metals by all-in-one ion exchange-nanofiltration membrane.

The composition of wastewater containing heavy metal mixtures is often complex and poses a serious threat to human and environmental health. Effective removal of a variety of heavy metal ions with a single technology is challenging, and the conventional split integrated technologies require multi-step processing and a massive footprint. For the first time, we achieve hierarchically integrating ion exchange and nanofiltration into all-in-one "iNF" membranes. The iNF membrane has a hierarchical structure with an interfacial polymerization layer and an ion exchange layer, which can achieve highly efficient indiscriminate heavy metal ion removal, overcoming the defect that traditional nanofiltration membranes can only remove single metal cations or oxyanions. The ion exchange layer can remove heavy metal ions through sulfonic acid groups and quaternary amine groups. In addition, the ion exchange layer can be regenerated by electro-deionization, which is meaningful for sustainable membrane usage. This facile, scalable, and compact integrated process shows outstanding potential and universal applicability in complex wastewater treatment.

Voltage-Gated Membranes Incorporating Cucurbit[n]uril Molecular Containers for Molecular Nanofiltration.

Smart voltage-gated nanofiltration membranes have enormous potential for on-demand and precise separation of similar molecules, which is an essential element of sustainable water purification and resource recovery. However, the existing voltage-gated membranes are hampered by limited selectivity, stability, and scalability due to electroactive monomer dimerization. Here, for the first time, the host-guest recognition properties of cucurbit[7]uril (CB[7]) are used to protect the viologen derivatives and promote their assembly into the membrane by interfacial polymerization. Viologen functions as a voltage switch, whereas CB[7] complexation prevents its dimerization and improves its redox stability. The inhibited diffusion of the CB[7]-viologen complex enables the precise patterning of the surface structure. The resultant voltage-gated membrane displays 80% improved rejection performance, excellent recovery accuracy for similar molecules, and anti-fouling properties. This work not only provides an innovative strategy for the preparation of voltage-gated smart nanofiltration membranes but also opens up new avenues for ion-selective transmission in water treatment, bionic ion channels, and energy conversion.

Metal Coordination Guided Formation of Discrete Neutral Three-Component Hydrogen-Bonded Architectures.

Interesting molecular architectures were obtained by combining heterodimeric quadruple hydrogen-bonding and neutral metal corner braces. The selection of cyclic and noncyclic aggregates from a random mixture of two-component assemblies has been achieved through metal coordination and careful adjustment of monomer rigidity and dimensions.

Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and Hydrogen Bonds.

We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal-coordinating 2,2'-bipyridine units. When mixed with metal ions such as Fe2+ or Zn2+, the tetrahedron cage complexes are formed in quantitative yields and full diastereoselectivity, even in highly polar acetonitrile or methanol solvents. The symmetry of the complexes obtained has been shown to depend critically on the flexibility of the ligand. Restriction of the rotation of the hydrogen-bonding unit with respect to the metal-coordinating site results in a T-symmetric cage, whereas introducing flexibility either through a methylene linker or rotating benzene ring allows the formation of S4-symmetric cages with self-filled interior. In addition, the possibility to select between tetrahedral cages or helicates and to control the dimensions of the aggregate has been demonstrated with a three-component assembly using external hydrogen-bonding molecular inserts or by varying the radius of the metal ion (Hg2+ vs Fe2+). Self-sorting studies of individual Fe2+ complexes with ligands of different sizes revealed their inertness toward ligand scrambling.

A Tautoleptic Approach to Chiral Hydrogen-Bonded Supramolecular Tubular Polymers with Large Cavity.

A new strategy towards tubular hydrogen-bonded polymers based on the self-assembly of isocytosine tautomers in orthogonal directions is proposed and experimentally verified, including by 1 H fast magic-angle spinning (MAS) solid-state NMR. The molecular tubes obtained possess large internal diameter and tailor-made outer functionalities rendering them potential candidates for a number of applications.

Stimuli-controlled self-assembly of diverse tubular aggregates from one single small monomer.

The design and synthesis of new stimuli-responsive hydrogen-bonding monomers that display a diversity of self-assembly pathways is of central importance in supramolecular chemistry. Here we describe the aggregation properties of a simple, intrinsically C2-symmetric enantiopure bicyclic cavity compound bearing a terminally unsubstituted ureidopyrimidinone fragment fused with a pyrrole moiety in different solvents and in the absence and presence of C60 and C70 guests. The tetrameric cyclic aggregate is selectively obtained in chlorinated solvents, where only part of the available hydrogen bonding sites are utilized, whereas in toluene or upon addition of C70 guests, further aggregation into tubular supramolecular polymers is achieved. The open-end cyclic assemblies rearrange into a closed-shell capsule upon introduction of C60 with an accompanied symmetry breaking of the monomer. Our study demonstrates that a C60 switch can be used to simultaneously control the topology and occupancy of tubular assemblies resulting from the aggregation of small monomers.

Water-soluble cavitands promote hydrolyses of long-chain diesters.

Water-soluble, deep cavitands serve as chaperones of long-chain diesters for their selective hydrolysis in aqueous solution. The cavitands bind the diesters in rapidly exchanging, folded J-shape conformations that bury the hydrocarbon chain and expose each ester group in turn to the aqueous medium. The acid hydrolyses in the presence of the cavitand result in enhanced yields of monoacid monoester products. Product distributions indicate a two- to fourfold relative decrease in the hydrolysis rate constant of the second ester caused by the confined space in the cavitand. The rate constant for the first acid hydrolysis step is enhanced approximately 10-fold in the presence of the cavitand, compared with control reactions of the molecules in bulk solution. Hydrolysis under basic conditions (saponification) with the cavitand gave >90% yields of the corresponding monoesters. Under basic conditions the cavitand complex of the monoanion precipitates from solution and prevents further reaction.

Macrocyclization of Folded Diamines in Cavitands.

Synthetic access to water-soluble cavitands and capsules has moved recognition events from organic solvents into aqueous media. Here we report the binding and reactivity of long-chain α,ω-diamines (C11 to C18) in cavitand hosts. The containers bind the diamines in folded conformations that bury the hydrocarbon chains and expose the amino groups to the aqueous medium. Their acylation with succinic anhydride results in improved yields of monofunctionalized products. The cavitand-bound amino acid products were cyclized to the corresponding macrocyclic dilactams in D2O using water-soluble carbodiimide. Direct reaction of the folded diamines in the cavitand with activated diesters of succinic acid and glutaric acids resulted in 54-96% yields of the 17- to 25-membered dilactams. These cavitand-chaperoned reactions provided 3- to 10-fold improvements over the yields obtained in bulk solution and offer an alternative to high dilution methods. The cavitand induces unlikely conformations in flexible guests and channels their reactivity along otherwise improbable paths.

A Remarkably Complex Supramolecular Hydrogen-Bonded Decameric Capsule Formed from an Enantiopure C2-Symmetric Monomer by Solvent-Responsive Aggregation.

The formation of an unprecedented decameric capsule in carbon disulfide, held together by the combination of double and triple hydrogen bonds between isocytosine units embedded in an enantiomerically pure bicyclic framework is reported. The aggregation occurs via symmetry breaking of the enantiopure intrinsically C2-symmetric monomer brought about by solvent, induced tautomerization of the hydrogen-bonding unit. We show that the topology of the aggregate is responsive to the solvent in which the assembly takes place. In this study we demonstrate that in carbon disulfide the chiral decameric cavity aggregate consisting of three forms of the same monomer, differing in their hydrogen bonding to each other is selectively formed, representing a tube-like structure capped with two C2-symmetric monomers. The large cylindrical cavity produced selectively accommodates one partially solvated C60 molecule, and molecular dynamic simulations revealed the special role of the solvent in the inclusion mechanism. The strategy described herein represents the first step toward the creation of a new class of hydrogen-bonded tubular objects from only one small symmetric building block by solvent-responsive aggregation.

Composition- and size-controlled cyclic self-assembly by solvent- and C60-responsive self-sorting.

Synthesis, solvent-, and guest-controlled self-assembly, and self-sorting of new hydrogen-bonded chiral cavity receptors are reported. The design of the cavity is based on the cyclic self-aggregation of monomers containing the 4H-bonding ureidopyrimidinone motif fused with the bicylo[3.3.1]nonane framework. Selective formation of kinetically inert cyclic tetramers is observed in chloroform, while in toluene an equilibrium between tetrameric and pentameric forms exists. The high affinity of the tetrameric aggregates toward C60 and C70 is observed in aromatic solvents. The host-guest interaction of unconventional π-acidic supramolecular receptors for fullerenes is turned off and on by changing the solvent, whereas the selection of size and the very composition of the cavity aggregate is controlled by either the change of solvent or the addition of fullerene guest, making our systems a new type of self-sorting device.