Anthracene-induced formation of highly twisted metallacycle and its crystal structure and tunable assembly behaviors.

Polycyclic aromatic hydrocarbons (PAHs) continue to attract increasing interest with respect to their applications as luminescent materials. The ordered structure of the metal-organic complex facilitates the selective integration of PAHs that can be tuned to function cooperatively. Here, a unique highly twisted anthracene-based organoplatinum metallacycle was prepared via coordination-driven self-assembly. Single-crystal X-ray diffraction analysis revealed that the metallacycle was twisted through the cooperation of strong π···π stacking interactions and steric hindrance between two anthracene-based ligands. Notably, the intramolecular twist and aggregation behavior introduced restrictions to the conformational change of anthracenes, which resulted in increased emission intensity of the metallacycle in solution. The emission behaviors and suprastructures based on the highly twisted metallacycle can be modulated by the introduction of different solvents. This study demonstrates that this metallacycle with highly twisted structure is a promising candidate for sensing and bioimaging applications.

Resorcinarene Induced Assembly of Carotene and Lutein into Hierarchical Superstructures.

The manipulation of carotenoid-based hierarchical superstructures affords attractive properties that facilitate application in biology and photosynthesis. Here, tubular suprastructures formed from water-soluble amide-modified resorcinarene and ß-carotene were reported, whereas microsheets were formed when ß-carotene was replaced with lutein. These structures were characterized using various measurements, indicating the differences of binding sites between resorcinarene and ß-carotene/lutein. Subsequently, the assembly mechanism was described by calculating the formation energy of the assemblies.

ß-Cyclodextrin modified Pt(II) metallacycle-based supramolecular hyperbranched polymer assemblies for DOX delivery to liver cancer cells.

Despite the widespread clinical application of chemotherapeutic anticancer drugs, their adverse side effects and inefficient performances remain ongoing issues. A drug delivery system (DDS) designed for a specific cancer may therefore overcome the drawbacks of single chemotherapeutic drugs and provide precise and synergistical cancer treatment by introducing exclusive stimulus responsiveness and combined chemotherapy properties. Herein, we report the design and synthesis of a supramolecular drug delivery assembly 1 constructed by orthogonal self-assembly technique in aqueous media specifically for application in liver cancer therapy. Complex 1 incorporates the ß-cyclodextrin host molecule-functionalized organoplatinum(II) metallacycle 2 with two specific stimulus-responsive motifs to the signaling molecule nitric oxide (NO), in addition to the three-armed polyethylene glycol (PEG) functionalized ferrocene 3 with redox responsiveness. With this molecular design, the particularly low critical aggregation concentration (CAC) of assembly 1 allowed encapsulation of the commercial anticancer drug doxorubicin (DOX). Controlled drug release was also achieved by morphological transfer via a sensitive response to the endogenous redox and NO stimuli, which are specifically related to the microenvironment of liver tumor cells. Upon combination of these properties with the anticancer ability from the platinum acceptor, in vitro studies demonstrated that DOX-loaded 1 is able to codeliver anticancer drugs and exhibit therapeutic effectiveness to liver tumor sites via a synergistic effect, thereby revealing a potential DDS platform for precise liver cancer therapeutics.

Self-Assembled Fluorescent Pt(II) Metallacycles as Artificial Light-Harvesting Systems.

Light-harvesting is one of the key steps in photosynthesis, but developing artificial light-harvesting systems (LHSs) with high energy transfer efficiencies has been a challenging task. Here we report fluorescent hexagonal Pt(II) metallacycles as a new platform to fabricate artificial LHSs. The metallacycles (4 and 5) are easily accessible by coordination-driven self-assembly of a triphenylamine-based ditopic ligand 1 with di-platinum acceptors 2 and 3, respectively. They possess good fluorescence properties both in solution and in the solid state. Notably, the metallacycles show aggregation-induced emission enhancement (AIEE) characteristics in a DMSO-H2O solvent system. In the presence of the fluorescent dye Eosin Y (ESY), the emission intensities of the metallacycles decrease but the emission intensity of ESY increases. The absorption spectrum of ESY and the emission spectra of the metallacycles show a considerable overlap, suggesting the possibility of energy transfer from the metallacycles to ESY, with an energy transfer efficiency as high as 65% in the 4a+ESY system.

Biomedically Relevant Self-Assembled Metallacycles and Metallacages.

Diverse metal-organic complexes (MOCs), shaped as rectangles, triangles, hexagons, prisms, and cages, can be formed by coordination between metal ions (Pt, Pd, Ru, Rh, Ir, Zn, Co, and Cd) and organic ligands, with potential applications as alternatives to conventional biomedical materials for therapeutic, sensing, and imaging purposes. MOCs have been investigated as anticancer drugs in the treatment of malignant tumors in lung, cervical, breast, colon, liver, prostate, ovarian, brain, stomach, bone, skin, mouth, thyroid, and other cancers. MOCs with one, two, and three cavities have also been investigated as drug carriers and prepared for the loading and release of different drugs. In addition, MOCs can target proteins by the shape effect and recognize sugars and DNA by electrostatic interactions, as well as estradiol by host-guest interactions, etc. This Perspective mainly covers achievements in the biomedical application of MOCs. We aim to identify some key trends in the reported MOC structures in relation to their biomedical activity and potential applications.

Spontaneous Supramolecular Polymerization Driven by Discrete Platinum Metallacycle-Based Host-Guest Complexation.

Considerable progress in platinum metallacycle-based supramolecular polymerization has promoted the fabrication and application of supramolecular materials. However, despite recent advances, supramolecular polymers constructed through platinum metallacycle-based host-guest complexation remain rare because of the dynamics of platinum metallacycles. Here, we achieve linear supramolecular polymerization via platinum metallacycle-based host-guest complexation by following the design rule of suppressing the dynamics of the metallacycles. The establishment of the platinum metallacycle-based host-guest system and the realization of this type of supramolecular polymerization are expected to open opportunities for platinum metallacycle-based functional materials.

Fluorescent Metallacage-Core Supramolecular Polymer Gel Formed by Orthogonal Metal Coordination and Host-Guest Interactions.

Herein, we report the preparation of a multifunctional metallacage-core supramolecular gel by orthogonal metal coordination and host-guest interactions. A tetragonal prismatic cage with four appended 21-crown-7 (21C7) moieties in its pillar parts was first prepared via the metal-coordination-driven self-assembly of cis-Pt(PEt3)2(OTf)2, tetraphenylethene (TPE)-based sodium benzoate ligands and linear dipyridyl ligands. Further addition of a bisammonium linker to the cage delivered a supramolecular polymer network via the host-guest interactions between the 21C7 moieties and ammonium salts, which formed a supramolecular gel at relatively higher concentrations. Due to the incorporation of a TPE derivative as the fluorophore, the gel shows emission properties. Multiple stimuli responsiveness and good self-healing properties were also observed because of the dynamic metal coordination and host-guest interactions used to stabilize the whole network structure. Moreover, the storage and loss moduli of the gel are 10-fold those of the gel without the metallacage cores, indicating that the rigid metallacage plays a significant role in enhancing the stiffness of the gel. The studies described herein not only enrich the functionalization of fluorescent metallacages via elegant ligand design but also provide a way to prepare stimuli-responsive and self-healing supramolecular gels as robust and smart materials.

Concentration-dependent supramolecular patterns of C3 and C2 symmetric molecules at the solid/liquid interface.

Here we report on a scanning tunnelling microscopy (STM) investigation on the self-assembly of C3- and C2-symmetric molecules at the solution/graphite interface. 1,3,5-tris((E)-2-(pyridin-4-yl)vinyl)benzene and 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethane are used as model systems. These molecules displayed a concentration dependent self-assembly behaviour on graphite, resulting in highly ordered supramolecular structures, which are stabilized jointly by van der Waals substrate-adsorbate interactions and in-plane intermolecular H-bonding. Denser packing is obtained when applying a relatively high concentration solution to the basal plane of the surface whereas a less dense porous network is observed upon lowering the concentration. We show that the molecular conformation does not influence the stability of the self-assembly and a twisted molecule can pack into dense and porous architectures under the concentration effect.

Near-Infrared Emissive Discrete Platinum(II) Metallacycles: Synthesis and Application in Ammonia Detection.

Two novel discrete organoplatinum(II) metallacycles are prepared by means of coordination-driven self-assembly of a 90° organoplatinum(II) acceptor, cis-(PEt3)2Pt(OTf)2, with two donors, a pyridyl donor, 9,10-di(4-pyridylvinyl)anthracene, and one of two dicarboxylate ligands. Both metallacycles display aggregation-induced emission as well as solvatochromism. More interestingly, both metallacycles exhibit near-infrared fluorescent emission in the solid state and can be used to detect ammonia gas.

Fe-Pt Twisted Heterometallic Bicyclic Supramolecules via Multicomponent Self-Assembly.

Herein, we describe a novel multicomponent self-assembly approach that has the prospect of furnishing unprecedented heterometallic bicyclic architectures with a high level of constitutional control. The methodology relies on the coordination directionality, and the stoichiometry of the individual precursor units, as well as on the difference of the coordination preference of the associated metal ions. As a proof-of-concept example, two aesthetically pleasing Fe-Pt heterometallic bicyclic metallacycles 6a and 6b, consisting of nine communicative components from four unique species, were prepared in ca. 70% isolated yields and fully characterized by multinuclear NMR, 2D NMR, electrospray ionization time-of-flight mass, and UV-vis spectroscopies. Furthermore, density functional theory based computations suggest that each of these supramolecular constructs encompasses two twisted [organo-Pt(II)←pyridine] coordination based irregular hexagons that are joined via a robust [terpyridine→Fe(II)←terpyridine] hinge.

Oxidative addition reaction of diarylplatinum(II) complexes with MeI in ionic liquid media: a kinetic study.

A kinetic study of the oxidative addition reaction of diarylplatinum(II) complexes [Pt(p-MeC(6)H(4))(2)(NN)] (1a: NN = 1,10-phenanthroline (phen) and 1b: NN = 4,4'-di-tert-butyl-2,2'-bipyridine ((t)Bu(2)bpy)) with MeI in ionic liquids 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][bta]) or 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) is described. The reactions were investigated as a function of MeI concentration and temperature under pseudo-first-order conditions using UV-vis spectroscopy techniques. In general, the oxidative addition reactions in ionic liquids followed an S(N)2 mechanism, similar to that reported for the related reactions in conventional solvents, e.g. benzene or acetone. The reaction rates in different solvents followed the order acetone > ionic liquids > benzene. The trend in the values of k(2) clearly indicated that ionic liquids behave like conventional solvents and that no particular 'ionic liquid effect' was detected in this kind of reaction. The effect of solvent on the reactions was examined using a linear solvation energy relationship (LSER) based on the Kamlet-Taft solvent scale. The activation parameters, DeltaH(++) and DeltaS(++), were obtained for the reactions in each solvent and the investigation of enthalpy-entropy compensation confirmed that the mechanism operated in all solvents is similar.