Synergizing Steric Hindrance and Stacking Interactions to Facilitate the Controlled Assembly of Multiple 41 Metalla-Knots and Pseudo-Solomon Links.

In this work, a noncoplanar terphenyl served as building block to synthesize a novel 3,3'-substituted bipyridyl ligand (L1) which further reacted with binuclear half-sandwich units A/B, giving rise to two aesthetical 41 metalla-knots in high yields via coordination-driven self-assembly strategy. Furthermore, given the inherent compactness of the 41 metalla-knots, it creates favorable conditions for the emergence of steric repulsion. We focused on progressively introducing nitrogen atoms featuring lone pair electrons (LPEs) into ligand L1 to manipulate the balance of H···H/LPEs···LPEs steric repulsion during the assembly process, ultimately achieving controlled assembly from 41 metalla-knots to the pseudo-Solomon link and then to molecular tweezer-like assembly facilitated by stacking interactions. All the assemblies were well characterized by solution-state NMR techniques, ESI-TOF/MS, and single-crystal X-ray diffraction. The evolutionary process of topological architectures is equivalent to visualizing the synergistic effect of steric hindrance and stacking interactions on structural assembly, providing a new avenue for achieving the controlled synthesis of different topologies.

The codriven assembly of molecular metalla-links ([Formula: see text], [Formula: see text]) and metalla-knots ([Formula: see text], [Formula: see text]) via coordination and noncovalent interactions.

Although mechanically interlocked molecules (MIMs) display unique properties and functions associated with their intricate connectivity, limited assembly strategies are available for their synthesis. Herein, we presented a synergistic assembly strategy based on coordination and noncovalent interactions (π-π stacking and CH⋯π interactions) to selectively synthesize molecular closed three-link chains ([Formula: see text] links), highly entangled figure-eight knots ([Formula: see text] knots), trefoil knot ([Formula: see text] knot), and Borromean ring ([Formula: see text] link). [Formula: see text] links can be created by the strategic assembly of nonlinear multicurved ligands incorporating a furan or phenyl group with the long binuclear half-sandwich organometallic Cp*RhIII (Cp* = η5-pentamethylcyclopentadienyl) clip. However, utilizing much shorter binuclear Cp*RhIII units for union with the 2,6-naphthyl-containing ligand led to a [Formula: see text] knot because of the increased π-π stacking interactions between four consecutive stacked layers and CH⋯π interactions. Weakening such π-π stacking interactions resulted in a [Formula: see text] knot. The universality of this synergistic assembly strategy for building [Formula: see text] knots was verified by utilizing a 1,5-naphthyl-containing ligand. Quantitative conversion between the [Formula: see text] knot and the simple macrocycle species was accomplished by adjusting the concentrations monitored by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Furthermore, increasing the stiff π-conjugated area of the binuclear unit afforded molecular Borromean ring, and this topology is a topological isomer of the [Formula: see text] link. These artificial metalla-links and metalla-knots were confirmed by single-crystal X-ray diffraction, NMR and ESI-MS. The results offer a potent strategy for building higher-order MIMs and emphasize the critical role that noncovalent interactions play in creating sophisticated topologies.

Introducing Frustrated Lewis Pairs to Metal-Organic Framework for Selective Hydrogenation of N-Heterocycles.

Hydrogenated nitrogen heterocyclic compounds play a critical role in the pharmaceutical, polymer, and agrochemical industries. Recent studies on partial hydrogenation of nitrogen heterocyclic compounds have focused on costly and toxic precious metal catalysts. As an important class of main-group catalysts, frustrated Lewis pairs (FLPs) have been widely applied in catalytic hydrogenation reactions. In principle, the combination of FLPs and metal-organic framework (MOF) is anticipated to efficiently enhance the recyclability performance of FLPs; however, the previously studied MOF-FLPs showed low reactivity in the hydrogenation of N-heterocycles compounds. Herein, we offer a novel P/B type MOF-FLP catalyst that was achieved via a solvent-assisted linker incorporation approach to boost catalytic hydrogenation reactions. Using hydrogen gas under moderate pressure, the proposed P/B type MOF-FLP can serve as a highly efficient heterogeneous catalyst for selective hydrogenation of quinoline and indole to tetrahydroquinoline and indoline-type drug compounds in high yield and excellent recyclability.

Flexible Vertex Engineers the Controlled Assembly of Distorted Supramolecular Tetrahedral and Octahedral Cages.

Designing and building unique cage assemblies attract increasing interest from supramolecular chemists but remain synthetically challenging. Herein, we propose the use of a flexible vertex with adjustable angles to selectively form highly distorted tetrahedral and octahedral cages, for the first time, in which the flexible vertex forms from the synergistic effect of coordination and covalent interactions. The inherent interligand angle of the vertex can be modulated by guest anions present, which allows for the fine-tuning of different cage geometries. Furthermore, the reversible structural transformation between tetrahedral and octahedral cages was achieved by anion exchange monitored by mass spectrometric technique, the smaller anions favoring tetrahedral cages, while the larger anions supporting octahedral cages. Additionally, the KBr-based cage thin films exhibited prominent enhancement of their third-order NLO responses in two or three orders of magnitude compared to those obtained for their corresponding solutions. This work not only provides a new methodology to build irregular polyhedral structures in a controlled and tunable way but also provides access to new kinds of promising functional optical materials.

Heterobimetallic Cluster-Based Coordination Polymers: Assembly, Structures and Third-Order Nonlinear Optical Properties.

Reactions of (NH4 )2 WS4 with CuCN, CuCN/1,2-bis(4-pyridyl)propane (bppa) or [Cu(MeCN)4 ]PF6 /bppa under different reaction conditions afforded a set of two- or three-dimensional W/Cu/S cluster-based coordination polymers including {[Et4 N]2 [WS4 Cu4 (µ-CN)2 (µ-I)2 ]}n (1), [WS4 Cu4 (µ-CN)2 (bppa)2 ]n (2) and {[WS4 Cu4 (bppa)4 ](PF6 )2 }n (3), respectively. Compound 2 can be readily formed from reaction of 1 with bppa under solvothermal conditions. Compounds 1 and 2 feature two-dimensional networks with a "sql" topology, while 3 possesses a two-fold interpenetrated three-dimensional net with a rare "reo" topology. Compounds 1-3 in DMF exhibited different third-order nonlinear optical responses, and they all showed a reverse saturable absorption while 2 held a strong self-focusing effect.

The Covalent and Coordination Co-Driven Assembly of Supramolecular Octahedral Cages with Controllable Degree of Distortion.

Discovering and constructing novel and fancy structures is the goal of many supramolecular chemists. In this work, we propose an assembly strategy based on the synergistic effect of coordination and covalent interactions to construct a set of octahedral supramolecular cages and adjust their degree of distortion. Our strategy innovatively utilizes the addition of sulfur atoms of a metal sulfide synthon, [Et4N][Tp*WS3] (A), to an alkynyl group of a pyridine-containing linker, resulting in a novel vertex with low symmetry, and of Cu(I) ions. By adjusting the length of the linker and the position of the reactive alkynyl group, the control of the deformation degree of the octahedral cages can be realized. These supramolecular cages exhibit enhanced third-order nonlinear optical (NLO) responses. The results offer a powerful strategy to construct novel distorted cage structures as well as control the degree of distortion of supramolecular geometries.