Ultra-High Metal-Ion Selectivity Induced by Intramolecular Cation-π Interactions for the One-Pot Synthesis of Precise Heterometallic Architectures.

Heterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host-guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than a statistical mixture, due to the limited metal-ion selectivity of coordination units. In particular, heterometallic architectures precisely encoded with different metal ions usually fail to form in a one-pot method when only one type of coordinated motif exists due to its poor metal-ion selectivity.

Coordination-Induced Conformational Control Enables Highly Luminescent Metallo-Cages.

In recent years, luminescent materials have received a great deal of attention due to their wide range of applications. However, exploring a simple solution to overcome the fluorescence quenching resulting from the aggregation of conventional organic fluorophores remains a valuable area of investigation. In this study, we successfully constructed two metallo-cages, namely, and , through coordination-driven self-assemblies of the triphenylamine (TPA)-based donor with different diplatinum(II) acceptors and , respectively.

A Highly Luminescent Metallo-Supramolecular Radical Cage.

Luminescent metal-radicals have recently received increasing attention due to their unique properties and promising applications in materials science. However, the luminescence of metal-radicals tends to be quenched after formation of metallo-complexes. It is challenging to construct metal-radicals with highly luminescent properties.

Construction of 1,3,5-Triazine-Based Prisms and Their Enhanced Solid-State Emissions.

In this study, two trigonal prisms based on the 1,3,5-triazine motif ( and ), distinguished by hydrophobic groups, were prepared by the self-assembly of tritopic terpyridine ligands and Zn(II) ions. and exhibited high luminescence efficiencies in the solid state, overcoming the fluorescence quenching of the 1,3,5-triazine group caused by π-π interactions. Notably, and exhibited different luminescence behaviors in the solution state and aggregation state.

Hourglass-Shaped Nanocages with Concaved Structures Based on Selective Self-Complementary Coordination Ligands and Tunable Hierarchical Self-Assembly.

Three-dimensional (3D) structures constructed via coordination-driven self-assemblies have recently garnered increasing attention due to the challenges in structural design and potential applications. In particular, developing new strategy for the convenient and precise self-assemblies of 3D supramolecular structures is of utmost interest. Introducing the concept of self-coordination ligands, herein the design and synthesis of two meta-modified terpyridyl ligands with selective self-complementary coordination moiety are reported and their capability to assemble into two hourglass-shaped nanocages SA and SB is demonstrated.

Dislocated Bilayer MOF Enables High-Selectivity Photocatalytic Reduction of CO to CO.

The highly selective photoreduction of CO into valuable small-molecule chemical feedstocks such as CO is an effective strategy for addressing the energy crisis and environmental problems. However, it remains a challenge because the complex CO photoreduction process usually generates multiple possible products and requires a subsequent separation step. In this paper, 2D monolayer and bilayer porphyrin-based metal-organic frameworks (MOFs) are successfully constructed by adjusting the reaction temperature and solvent polarity with 5,10,15,20-tetrakis(4-pyridyl)porphyrin as the light-harvesting ligand.

Construction of metallo-triangles with -TPE motifs and fluorescence properties.

Two metallo-triangles, SA and SB, with -TPE motifs were constructed, and their fluorescence properties were explored. Compared with the dilute solution, both triangles SA and SB exhibited significant AIE behavior in the aggregated states. Moreover, the shorter version SA showed higher quantum yields than SB in the aggregated states.

Multi-Decker Emissive Supramolecular Architectures Based on Shape-Complementary Ligands Pair.

Dye aggregates have attracted a great deal of attention due to their widespread applications in organic light-emitting devices, light-harvesting systems, etc. However, the strategies to precisely control chromophores with specific spatial arrangements still remain a great challenge. In this work, a series of double- and triple-decker supramolecular complexes are successfully constructed by coordination-driven self-assembly of carefully designed shape-complementary ligands, one claw-like tetraphenylethylene (TPE)-based host ligand and three tetratopic or ditopic guest ligands.

Discrete Platinum(II) Metallacycles with Inner- and Outer-Modified 9,10-Distyrylanthracene: Design, Self-Assembly, and Luminescence Properties.

To completely unravel the relationship between structures and luminescence properties of inner- and outer-modified metallacycles, two rhombic metallacycles and with 9,10-distyrylanthracene (DSA) were constructed herein via the design of DSA moieties on the inside or outside of metallacycles. Similar building blocks of the two metallacycles led to the same emission wavelengths in a dilute solution. In contrast, their fluorescence emissions in the aggregation and solid states were significantly different and revealed interesting emission behaviors from structures with inner- and outer-modified design.

Design and Self-Assembly of Macrocycles with Metals at the Corners Based on Dissymmetric Terpyridine Ligands.

Terpyridine-based discrete supramolecular architectures with metal ions at the corners have rarely been reported. Herein, we report two dissymmetric terpyridyl ligands LA and LB decorated at the 5-position and 4-position of terpyridine respectively. The complexes constructed by the self-assembly of LA and LB with Zn(II) exhibit hand-circle-like structures.

Conformational Control of a Metallo-Supramolecular Cage via the Dissymmetrical Modulation of Ligands.

In nature as well as life systems, the presence of asymmetrical and dissymmetrical structures with specific functions is extremely common. However, the construction of metallo-supramolecular assemblies based on dissymmetrical ligands still remains a considerable challenge for avoiding the generation of unexpected isomers with similar thermodynamic stabilities, especially for three-dimensional supramolecular structures. In this study, a strategy for the conformational control of metallo-supramolecular cages via the enhancement of ligand dissymmetry was proposed.

Self-Assembly Methods for Recently Reported Discrete Supramolecular Structures Based on Terpyridine.

In this Review, self-assembly methods of discrete metallo-supramolecules based on 2,2' : 6',2''-terpyridine (tpy) are comprehensively summarized. With the development of self-assembly, strategies for discrete 2D and 3D supramolecular architectures have boomed, including the geometry-directed method, template-driven method, and stepwise method. Ligand geometry-directed method mainly depends on the geometry of ligands (i.

Designing narcissistic self-sorting terpyridine moieties with high coordination selectivity for complex metallo-supramolecules.

Coordination-driven self-assembly is a powerful approach for the construction of metallosupramolecules, but designing coordination moieties that can drive the self-assembly with high selectivity and specificity remains a challenge. Here we report two ortho-modified terpyridine ligands that form head-to-tail coordination complexes with Zn(II). Both complexes show narcissistic self-sorting behaviour.

Self-Assembly of Metallo-Supramolecules with Dissymmetrical Ligands and Characterization by Scanning Tunneling Microscopy.

Asymmetrical and dissymmetrical structures are widespread and play a critical role in nature and life systems. In the field of metallo-supramolecular assemblies, it is still in its infancy for constructing artificial architectures using dissymmetrical building blocks. Herein, we report the self-assembly of supramolecular systems based on two dissymmetrical double-layered ligands.

From Dimeric to Octameric Metallo-Supramolecular Macrocycles Based on Sterically Congested Ligand-assisted Self-Assembly with Zn(II), Cd(II), and Fe(II).

Two sterically congested 2,2':6',2″-terpyridine-based ligands LA and LB, composed of asymmetrically contiguous terpyridine units, are designed and synthesized for metallo-supramolecular architectures. The significant advantage of this design is that the terpyridines in these ligands have different chemical environments and show a selective coordination ability with each other. For ditopic ligand LA, the self-assembly with Zn(II), Cd(II), and Fe(II) gave the rhombic dimers, which have the same sets of terpyridine signals as ligand LA.

Stepwise Self-Assembly and Dynamic Exchange of Supramolecular Snowflakes.

Snowflake, a highly symmetrical hexagram figure, is challenging to be expressed by chemistry/supramolecular chemistry due to the complex structure. Herein, we have constructed super snowflake supramolecules using terpyridine (tpy)-based metal-organic building blocks with and connectivities through stepwise strategies in high yield. The structures were characterized by multi-dimensional mass spectrometry and multi-dimensional NMR spectrometry.

Stepwise Self-Assembly and Dynamic Exchange of Supramolecular Nanocages Based on Terpridine Building Blocks.

Coordination-driven self-assembly as a powerful bottom-up approach has been extensively used to construct multifarious supramolecular architectures with increasing complexity and functionality. Due to the unique cavity structures and precisely controllable dimensions, 3D supramolecules display unprecedented properties and functions in catalysis, sensing, gas storage, and smart materials. Herein, we have built two 3D nanocages with different sizes by changing the length of the organic ligand arms.

Components in melanoma cytoplasm might induce murine BMSCs transformation and expression of Melan-A.

This study explored the possibility that the components in melanoma cytoplasm induce murine BMSCs transformation and expression of Melan-A by morphologically observing the changes of BMSCs and immunocytochemically detecting Melan-A in the cells after culturing BMSCs in medium containing melanoma cytoplasm components (MCC). MCC of B16 melanoma cells was prepared and BMSCs were cultured and induced by adding the MCC into culture medium. The cells were morphologically observed and Melan-A was immunohistochemically detected to confirm BMSCs transformation.