The impact of aggregation of AIE and ACQ moiety-integrating material on the excited state dynamics.

The investigation of the properties of aggregate materials is highly interesting because the process of aggregation can result in the disappearance of original properties and the emergence of new ones. Here, a novel fluorescent material (TPEIP), which synergistically combines aggregation-induced emission (AIE) and aggregation caused quenching (ACQ) moieties, was first synthesized by the cyclization reaction of 2,3-diamino-phenazine with 4-tetraphenylenthenealdehyde. We controlled the degree of aggregation of TPEIP to shed light on the impact of the aggregation on the excited state dynamics. TPEIP aggregation realized control over the Intersystem Crossing (ISC) rates and, in turn, the suppression of triplet excited states in MeOH, EtOH or via the simple addition of water to TPEIP solutions in DMSO. From global target analysis, the time scale was 966.2 ps for ISC for TPEIP in DMSO, but it was 860 ps in the case of TPEIP solutions featuring 5% water. The dynamics of TPEIP excited states undergo significant changes as the degree of aggregation increases. Notably, the lifetime of singlet excited states decreases, and there was a gradual diminishment in triplet states.

Self-Assembly of [3]Catenane and [4]Catenane Based on Neutral Organometallic Scaffolds.

Transition metal-mediated templating and self-assembly have shown great potential to construct mechanically interlocked molecules. Herein, we describe the formation of the bimetallic [3]catenane and [4]catenane based on neutral organometallic scaffolds via the orthogonality of platinum-to-oxygen coordination-driven self-assembly and copper(I) template-directed strategy of a [2]pseudorotaxane. The structures of these bimetallic [3]catenane and [4]catenane were characterized by multinuclear NMR {1H and 31P} spectroscopy, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and PM6 semiempirical molecular orbital theoretical calculations. In addition, single-crystal X-ray analyses of the [3]catenane revealed two asymmetric [2]pseudorotaxane units inside the metallacycle. It was discovered that tubular structures were formed through the stacking of individual [3]catenane molecules driven by the strong π-π interactions.

Acid-Activated Motion Switching of DB24C8 between Two Discrete Platinum(II) Metallacycles.

The precise operation of molecular motion for constructing complicated mechanically interlocked molecules has received considerable attention and is still an energetic field of supramolecular chemistry. Herein, we reported the construction of two tris[2]pseudorotaxanes metallacycles with acid-base controllable molecular motion through self-sorting strategy and host-guest interaction. Firstly, two hexagonal Pt(II) metallacycles M1 and M2 decorated with different host-guest recognition sites have been constructed via coordination-driven self-assembly strategy. The binding of metallacycles M1 and M2 with dibenzo-24-crown-8 (DB24C8) to form tris[2]pseudorotaxanes complexes TPRM1 and TPRM2 have been investigated. Furthermore, by taking advantage of the strong binding affinity between the protonated metallacycle M2 and DB24C8, the addition of trifluoroacetic acid (TFA) as a stimulus successfully induces an acid-activated motion switching of DB24C8 between the discrete metallacycles M1 and M2. This research not only affords a highly efficient way to construct stimuli-responsive smart supramolecular systems but also offers prospects for precisely control multicomponent cooperative motion.

Controlled Self-Assembly of Metallacycle-Bridged Gold Nanoparticles for Surface-Enhanced Raman Scattering.

In this work, well-defined two-dimensional metallacycles have been successfully employed for the well-controlled self-assembly of gold nanoparticles (AuNPs) into discrete clusters such as dimers, trimers, tetramers, pentamers and even hexamers at the water-oil interface for the first time. Furthermore, the modular construction of metallacycle molecules allows precise control of spacing between the gold nanoparticles. Interestingly, it was found that interparticle spacing below 5 nm created by molecular metallacycles in the resultant discrete gold nanoparticle clusters led to a strong plasmon coupling, thus inducing great field enhancement inside the gap between the NPs. More importantly, different discrete clusters with precise interparticle spacing provide a well-defined system for studying the hot-spot phenomenon in surface-enhanced Raman scattering (SERS); this revealed that the SERS effects were closely related to the interparticle spacing.

Efficient self-assembly of heterometallic triangular necklace with strong antibacterial activity.

Sophisticated mechanically interlocked molecules (MIMs) with interesting structures, properties and applications have attracted great interest in the field of supramolecular chemistry. We herein report a highly efficient self-assembly of heterometallic triangular necklace 1 containing Cu and Pt metals with strong antibacterial activity. Single-crystal X-ray analysis shows that the finely arranged triangular necklace 1 has two racemic enantiomers in its solid state with intriguing packing motif. The superior antibacterial activity of necklace 1 against both standard and clinically drug-resistant pathogens implies that the presence of Cu(I) center and platinum(II) significantly enhance the bacterium-binding/damaging activity, which is mainly attributed to the highly positively charged nature, the possible synergistic effect of heterometals in the necklace, and the improved stability in culture media. This work clearly discloses the structure-property relationships that the existence of two different metal centers not only facilitates successful construction of heterometallic triangular necklace but also endows it with superior nuclease properties and antibacterial activities.

Hierarchical self-assembly of discrete bis-[2]pseudorotaxane metallacycle with bis-pillar[5]arene via host-guest interactions and their redox-responsive behaviors.

A discrete rhomboidal metallacycle R functionalized with bis-[2]pseudorotaxane of [Cu(phenanthroline)2]+ derivatives was successfully synthesized via coordination-driven self-assembly. Furthermore, the host-guest complexation of such a bis-[2]pseudorotaxane metallacycle with a bis-pillar[5]arene (bisP5) allowed for the formation of a new family of cross-linked supramolecular polymers R⊃(bisP5)2, which displayed interesting redox-responsive properties. By taking advantage of the substantial structural differences between the coordination geometries of [Cu(phenanthroline)2]+ and [Cu(phenanthroline)2]2+, the weight-average diffusion coefficients D of the supramolecular polymer were adjusted through changing the redox state of the Cu(i)/Cu(ii) complexes.

Radical-Induced Hierarchical Self-Assembly Involving Supramolecular Coordination Complexes in Both Solution and Solid States.

To explore a new supramolecular interaction as the main driving force to induce hierarchical self-assembly (HSA) is of great importance in supramolecular chemistry. Herein, we present a radical-induced HSA process through the construction of well-defined rhomboidal metallacycles containing triphenylamine (TPA) moieties. The light-induced radical generation of the TPA-based metallacycle has been demonstrated, which was found to subsequently drive hierarchical self-assembly of metallacycles in both solution and solid states. The morphologies of nanovesicle structures and nanospheres resulting from hierarchical self-assembly have been well-illustrated by using TEM and high-angle annular dark-field STEM (HAADF-STEM) micrographs. The mechanism of HSA is supposed to be associated with the TPA radical interaction and metallacycle stacking interaction, which has been supported by the coarse-grained molecular dynamics simulations. This study provides important information to understand the fundamental TPA radical interaction, which thus injects new energy into the hierarchical self-assembly of supramolecular coordination complexes (SCCs). More interestingly, the stability of TPA radical cations was significantly increased in these metallacycles during the hierarchical self-assembly process, thereby opening a new way to develop stable organic radical cations in the future.

Supramolecular Polymer Cross-Linked by Discrete Tris-[2]pseudorotaxane Metallacycles and Its Redox-Responsive Behavior.

A new discrete hexagonal metallacycle M containing tris-[2]pseudorotaxane moiety has been successfully designed and synthesized via coordination-driven self-assembly. The newly designed tris-[2]pseudorotaxane metallacycle was well characterized with nuclear magnetic resonance and mass spectra analysis. Such tris-[2]pseudorotaxane metallacycle M and pillar[5]arene dimer (PD) could further form a new family of cross-linked redox-responsive supramolecular polymer M⊃(PD)3 through a host-guest interaction. Interestingly, the polymer M⊃(PD)3 displayed redox-responsive behavior and showed tuned weight-average diffusion coefficients D upon redox stimuli, which is attributed to the changed coordination geometries of [Cu(phen)2]+ and [Cu(phen)2]2+ in such system.

Colorimetric and fluorescent chemosensor for highly selective and sensitive relay detection of Cu2+ and H2PO4- in aqueous media.

In this manuscript, a new colorimetric and fluorescent chemosensor (T) was designed and synthesized, it could successively detect Cu2+ and H2PO4- in DMSO/H2O (v/v=9:1, pH=7.2) buffer solution with high selectivity and sensitivity. When added Cu2+ ions into the solution of T, it showed a color changes from yellow to colorless, meanwhile, the green fluorescence of sensor T quenched. This recognition behavior was not affected in the presence of other cations, including Hg2+, Ag+, Ca2+, Co2+, Ni2+, Cd2+, Pb2+, Zn2+, Cr3+, and Mg2+ ions. More interestingly, the Cu2+ ions contain sensor T solution could recover the color and fluorescence upon the addition of H2PO4- anions in the same medium. And other surveyed anions (including F-, Cl-, Br-, I-, AcO-, HSO4-, ClO4-, CN- and SCN-) had nearly no influence on the recognition behavior. The detection limits of T to Cu2+ and T-Cu2+ to H2PO4- were evaluated to be 1.609×10-8M and 0.994×10-7M, respectively. In addition, the sensor T also could be served as a recyclable component and the logic gate output was also defined in sensing materials. The test strips based on sensor T were fabricated, which acted as a convenient and efficient Cu2+ and H2PO4- test kits.

A "keto-enol tautomerization"-based response mechanism: a novel approach to stimuli-responsive supramolecular gel.

A novel approach to stimuli-responsive gel termed the "keto-enol tautomerization"-based response mechanism was proposed. By tautomerization, vinyl ketone-based gelator G3 can be self-assembled into an organogel (OG3) accompanied by strong AIE. OG3 shows reversible dual-channel response for S(2-). The response process is based on the reversible deprotonation of the enol moiety in the tautomerized gelator G3'.