The syntheses, characterization, and emission properties of three tetragonal prismatic cages, 4a-4c, constructed from eight 90° Pt(II) acceptors, four linear dipyridyl ligands, and two tetraphenylethene (TPE)-based sodium benzoate ligands, are described. These cages are emissive in dilute solutions due to the metal-coordination-induced partial restriction of intramolecular rotation of their TPE units, while the dipyridyl moieties, which act as the pillars as well as the solvents, strongly influence these emissions. Specifically, cages 4a and 4b, bearing a 4,4'-dipyridine and a 1,2-di(4-pyridyl)ethylene as their pillar parts, respectively, display good emissions in common organic solvents at 485-493 nm that are derived from the TPE units. In contrast, cage 4c, with its BODIPY-based dipyridyl unit, exhibits two emission bands at 462-473 and 540-545 nm, originating from the TPE and BODIPY fluorophores, respectively. Moreover, cage 4b has been employed as a turn-on fluorescent sensor for thiol-containing amino acids via a self-destructive reaction, while the cage can also be regenerated via the addition of Pt(II) acceptors. The studies described herein not only enrich the ongoing research on fluorescent materials but also pave the way to prepare stimuli-responsive supramolecular coordination complexes.

Over the past couple of decades, coordination-driven self-assembly has evolved as a broad multidisciplinary domain that not only covers the syntheses of aesthetically pleasing supramolecular architectures but also emerges as a method to form new optical materials, chemical sensors, theranostic agents, and compounds with light-harvesting and emissive properties. The majority of these applications depend upon investigations that reveal the photophysical nature and electronic structure of supramolecular coordination complexes (SCCs), including two-dimensional (2D) metallacycles and three-dimensional (3D) metallacages. As such, well-defined absorption and emission spectra are important for a given SCC to be used for sensing, bioimaging, and other applications with molecular fluorescence being an important component. In this Account, we summarize the photophysical properties of some bis(phosphine)organoplatinum(II) compounds and their discrete SCCs. The platinum(II) based organometallic precursors typically display spectral red-shifts and have low fluorescence quantum yields and short fluorescence lifetimes compared to their organic counterparts because the introduction of metal centers enhances both intersystem crossing (ISC) and intramolecular charge transfer (ICT) processes, which can compete with the fluorescence emissions. Likewise ligands with conjugation can also increase the ICT process; hence the corresponding organoplatinum(II) compounds undergo a further decrease in fluorescence lifetimes. The use of endohedral amine functionalized 120°-bispyridyl ligands can dramatically enhance the emission properties of the resultant organoplatinum(II) based SCCs. As such these SCCs display emissions in the visible region (ca. 400-500 nm) and are significantly red-shifted (ca. 80-100 nm) compared to the ligands. This key feature makes them suitable as supramolecular theranostic agents wherein these unique emission properties provide diagnostic spectroscopic handles and the organoplatinum(II) centers act as potential anticancer agents. Using steady state and time-resolved-spectroscopic techniques and quantum computations in concert, we have determined that the emissive properties stem from the ligand-centered transitions involving π-type molecular orbitals with modest contributions from the metal-based orbitals. The self-assembly and the photophysics of organoplatinum(II) ← 3-substituted pyridyl based SCCs are highly diverse. Subtle changes in the ligands' structures can form molecular congener systems with distinct conformational and photophysical properties. Furthermore, the heterometallic SCCs described herein possess rich photophysical properties and can be used for sensing based applications. Tetraphenylethylene (TPE) based SCCs display emissions in the aggregated state as well as in dilute solutions. This is a unique phenomenon that bridges the aggregation caused quenching (ACQ) and aggregation induced emission (AIE) effects. Moreover, a TPE based metallacage exhibits solvatoluminescence, including white light emiss...

Photodynamic therapy is an effective alternative to traditional treatments due to its minimally invasive nature, negligible systemic toxicity, fewer side effects, and avoidance of drug resistance. However, it is still challenging to design photosensitizers with high singlet oxygen (1O2) quantum yields (QY) due to severe aggregation of the hydrophobic photosensitizers. Herein, we developed a discrete organoplatinum(II) metallacage using therapeutic cis-(PEt3)2Pt(OTf)2 as the building block to improve the 1O2 QY, thus achieving synergistic anticancer efficacy. The metallacage-loaded nanoparticles (MNPs) with tri-modality imaging capability allow precise diagnosis of tumor and real-time monitoring the delivery, biodistribution, and excretion of the MNPs. MNPs exhibited excellent anti-metastatic effect and superior anti-tumor performance against U87MG, drug resistant A2780CIS, and orthotopic tumor models, ablating the tumors without recurrence after a single treatment. Gene chip analyses confirmed the contribution of different therapeutic modalities to the tumor abrogation. This supramolecular platform holds potential in precise cancer theranostics.

Hierarchical self-assembly (HAS) is a multilevel organization process that first assembles elementary molecular units into ordered secondary structures via noncovalent interactions, which further act as the building blocks to form more complex multifunctional superstructures at the next level(s). The HAS strategy has been used as a versatile method for the preparation of soft-matter nanoarchitectures of defined size and morphologies, tunable luminescence, and biological importance. However, such preparation can be greatly simplified if well-defined dynamic structures are employed as the cores that upon linking form the desired nanoarchitectures. Discrete supramolecular coordination complexes (SCCs) with well-defined shapes, sizes, and internal cavities have been widely employed to construct hierarchical systems with functional diversity. This Account summarizes the prevailing strategies used in recent years in the preparation of SCC-based HASs and illustrates how the combination of dynamic metal-ligand coordination with other interactions was used to obtain hierarchical systems with interesting properties. HASs with dual orthogonal interactions involving coordination-driven self-assembly and hydrogen bonding/host-guest interaction generally result in robust and flexible supramolecular gels. Likewise, hybridization of SCCs with a suitable dynamic covalent network via a hierarchical strategy is useful to prepare materials with self-healing properties. The intrinsic positive charges of the SCCs also make them suitable precursors for the construction of HASs via electrostatic interactions with negatively charged biological/abiological molecules. Furthermore, the interplay between the hydrophilic and lipophilic characters of HASs by varying the number and spacial orientation of alkyl/oxyethylene chains of the SCC is a simple yet controllable approach to prepare ordered and tunable nanostructures. Certain SCC-cored hierarchical systems exhibit reversible polymorphism, typically between micellar, nanofiber, and vesicular phases, in response to various external perturbations: heat, photoirradiation, pH-variance, redox-active agents, etc. At the same time, multiple noncovalent interaction mediated HASs are growing in numbers and are promising candidates for obtaining functionally diverse materials. The photophysical properties of SCC-based HASs have been used in many analytical applications. For example, embedding tetraphenylethene (TPE)-based pyridyl ligands within metallo-supramolecular structures partially restricts the molecular rotations of its phenyl rings, endowing the resultant SCCs with weak emissions. Further aggregation of such HASs in suitable solvents results in a marked enhancement in emission intensity along with quantum yields. They act as sensitive sensors for different analytes, including pathogens, drugs, etc. HASs are also useful to develop multidrug systems with cooperative chemotherapeutic effects. Hence, the use of HASs with theranostic SCCs combining cell-imaging agents and chemotherapeutic scaffol...

Materials that organize multiple functionally active sites, especially those with aggregation-induced emission (AIE) properties, are of growing interest due to their widespread applications. Despite promising early architectures, the fabrication and preparation of multiple AIEgens, such as multiple tetraphenylethylene (multi-TPE) units, in a single entity remain a big challenge due to the tedious covalent synthetic procedures often accompanying such preparations. Coordination-driven self-assembly is an alternative synthetic methodology with the potential to deliver multi-TPE architectures with light-emitting characteristics. Herein, we report the preparation of a new family of discrete multi-TPE metallacycles in which two pendant phenyl rings of the TPE units remain unused as a structural element, representing novel AIE-active metal-organic materials based on supramolecular coordination complex platforms. These metallacycles possess relatively high molar absorption coefficients but weak fluorescent emission under dilute conditions because of the ability of the untethered phenyl rings to undergo torsional motion as a non-radiative decay pathway. Upon molecular aggregation, the multi-TPE metallacycles show AIE-activity with markedly enhanced quantum yields. Moreover, on account of their AIE characteristics in the condensed state and ability to interact with electron-deficient substrates, the photophysics of these metallacycles is sensitive to the presence of nitroaromatics, motivating their use as sensors. This work represents a unification of themes including molecular self-assembly, AIE, and fluorescence sensing and establishes structure-property-application relationships of multi-TPE scaffolds. The fundamental knowledge obtained from the current research facilitates progress in the field of metal-organic materials, metal-coordination-induced emission, and fluorescent sensing.

Despite the well-known anticancer activity of mono- and multi-nuclear platinum complexes, studies of the antitumor performances of platinum-based supramolecular coordination complexes are rare. Herein, we report on the synthesis of a four-armed amphiphilic copolymer Pt-PAZMB-b-POEGMA containing a theranostic metallacycle M, in which the tetraphenylethene derivative acts as an aggregation-induced emissive fluorescent probe for live cell imaging and the 3,6-bis[trans-Pt(PEt3)2]phenanthrene (PhenPt) is an anticancer drug. This copolymer was further self-assembled into nanoparticles of different sizes and vesicles depending upon the experimental conditions. The impact of the morphology and size of the assemblies on their endocytic pathways, uptake rates, internalization amounts and cytotoxicities were fully investigated. The self-assemblies were further employed to encapsulate doxorubicin (DOX) to achieve a synergistic anticancer effect. Controlled drug release was also realized via amphiphilicity changes and was driven by a glutathione-induced cascade elimination reaction. The DOX-loaded nanoparticles of around 50 nm in size exhibited an excellent antitumor performance as well as a low systemic toxicity, due to an enhanced permeability and retention effect.

Over years, mathematicians, biologists and chemists have capitalised on the highly useful concept of orthogonality for developing sophisticated complex systems. The use of orthogonal pairs ensures that any modification made on one pair does not propagate any effect onto the other. While the concept equally pertains to dynamic supramolecular interactions, interference-free self-assembly built on multiple orthogonal interactions is still limited and the underlying notions are not yet firmly established. Herein, we identify, classify and evaluate dynamic interactions in various orthogonal settings in order to distill out general recommendations for reliable dynamic orthogonality. Our classification has to exclude templating, allosteric and/or cooperative effects as the latter are specific for individual cases only.

Herein, we describe the synthesis of tetraphenylethylene (TPE)-based di-Pt(II) acceptors as shown by X-ray analysis, which are subsequently used to construct pure TPE-based 2D hexagonal metallacycles and 3D drumlike metallacages with three different counteranions via coordination-driven self-assembly. The metallacycles possess alternating TPE donor and acceptor units that arrange 12 pendant phenyl rings along the outer perimeter that provide the basis for the observed aggregation-induced emission (AIE) behavior. The metallacages are similarly constructed from TPE-based building blocks, specifically two donors and four acceptors, resulting in eight freely rotating phenyl rings decorating the prismatic core. The fluorescence of these cages in dilute solution is intensified when hexane is added to CH2Cl2 solutions, indicative of aggregation-induced enhanced emission (AIEE). The influence of the counteranions on the photophysics of the assemblies was investigated. The molar absorption coefficients (ε), fluorescence emission intensities, and quantum yield (ΦF) values of the SCCs with different counteranions in CH2Cl2 follow the order PF6(-) > OTf(-) > NO3(-). The same trend also applies to the AIE characteristics of the SCCs in the aggregated state. The metal-organic materials developed here not only enrich a newly emerging library of self-assembly AIE metallacycles and cages that are promising candidates for turn-on fluorescent sensors and advanced optical devices but also provide an understanding of how structural factors affect the photophysics of AIE-active SCCs.