Chiral Self-Sorting, Spontaneous Resolution, and Hierarchical Self-Assembly in Metal-Organic Cages.

The ability to collectively program chiral recognition and the hierarchical self-assembly of molecular and supramolecular building blocks into complex higher-order superstructures is a significant goal in supramolecular chemistry. Metal-organic cages are excellent model systems to examine chiral self-sorting and build hierarchical self-assembly. Herein, details on how limiting the conformational flexibility and incorporating hydrogen bonding functional groups in the ligands can influence chiral self-sorting and hierarchical self-assembly of metal-organic cages are reported. The urea-functionalized axially chiral bis-pyridyl ligands afford high-fidelity in chiral self-sorting in Pd2L4 cages, when they have fewer conformations. Ligand L1, with more conformations, affords mixture of heterochiral and homochiral cages (≈70:30). Among them, the heterochiral cage adopts unusual twisted conformation and self-assembles into 2D sheets, linked by anion coordination between urea and nitrate. Ligand L2, with fewer conformations, affords homochiral cages via high-fidelity chiral self-sorting. The choice of counter anions influences further self-sorting in the solid state: racemate with PF6 - and spontaneously resolves conglomerate with BF4 -. Urea-BF4 hydrogen bonding directs hierarchical self-assembly of the Pd2L4 metal-organic cages into super-cubic networks. The study introduces a new approach in hierarchical self-assembly of metal-organic cages into higher-order networks aided by hydrogen bonding anion coordination with functional ligands.

Pyridine appended pyrimidine bis hydrazone: Zn2+/ATP detection, bioimaging and functional properties of its dinuclear Zn(II) complex.

A pyridine functionalized pyrimidine-based system, H2P was successfully synthesized, characterized, and evaluated for its remarkable selective characteristics towards Zn2+ and ATP ions. The chemical sensing capabilities of H2P were demonstrated through absorption, fluorescence, and NMR spectroscopic techniques. The probe exhibited outstanding sensitivity when interacting with the ions, demonstrating relatively strong association constants and impressively low detection limits. The comprehensive binding mechanism of H2P with respect to Zn2+ and ATP ions was investigated using a combination of analytical methods, including Job's plot, NMR spectroscopy, mass spectrometry, and density functional theory (DFT) experiments. The interesting sensing ability of H2P for Zn2+/ATP ions was harnessed for live cell bioimaging and other diverse on-site detection purposes, including paper strips, cotton swabs, and applications involving mung bean sprouts. Further, the fluorescent probe demonstrated its effectiveness in detecting Zn2+ and ATP within live cells, indicating its significant potential in the realm of biological imaging applications. Moreover, the molecular configuration of the zinc complex (H2P-Zn2Cl4), derived from H2P, was elucidated using X-ray crystallography. This complex exhibited intriguing multifunctional attributes, encompassing its capability for detecting picric acid and for reversible acid/base sensing responses. The enhanced conducting behavior of the complex as well as its resistance properties were investigated by performing I-V characteristics and electrochemical impedance spectroscopic (EIS) experiments respectively.

Conformationally Flexible Cleft Receptor for Chloride Anion Transport.

The design and synthesis of a cleft-shaped bis-diarylurea receptor for chloride anion transport is reported in this work. The receptor is based on the foldameric nature of N,N'-diphenylurea upon its dimethylation. The bis-diarylurea receptor exhibits a strong and selective affinity for chloride over bromide and iodide anions. A nanomolar quantity of the receptor efficiently transports the chloride across a lipid bilayer membrane as a 1:1 complex (EC50 = 5.23 nm). The work demonstrates the utility of the N,N'-dimethyl-N,N'-diphenylurea scaffold in anion recognition and transport.

Chiral Self-Sorting in Pd6 L12 Metal-Organic Cages.

Chiral self-sorting during the formation of cage-like molecules continues to fascinate and advance our understanding of the phenomenon in general. Herein, we report the chiral self-sorting in the Pd6 L12 -type metal-organic cages. When a racemic mixture of axially chiral bis-pyridyl ligands undergo coordination-driven self-assembly with Pd(II) ions to form Pd6 L12 -type cages, the system has the option of chiral self-sorting to afford any of at least 70 pairs of (one homochiral and 69 heterochiral) enantiomers and 5 meso isomers or a statistical mixture of everything. However, the system resulted in diastereoselective self-assembly through a high-fidelity chiral social self-sorting to form a racemic mixture of D3 symmetric heterochiral [Pd6 (L6R/6S )12 ]12+ /[Pd6 (L6S/6R )12 ]12+ cages.

Anion-Driven Programmable Chiral Self-Sorting in Metal-Organic Cages and Structural Transformations between Heterochiral and Homochiral Cages.

When a racemic mixture of chiral building blocks self-assembles to form discrete molecular or supramolecular cages, the system can adopt either social or narcissistic chiral self-sorting. However, control over such chiral self-sorting is hard to achieve with a desired choice of outcome. Herein, we report anion templated high-fidelity chiral self-sorting during the coordination-driven self-assembly of [Pd2 L4 ] metal-organic cages, with a racemic mixture of an axially chiral ligand. Upon varying the counter-anions, the outcome of the choice of chiral self-sorting, whether social or narcissistic, leading to kinetically favored heterochiral or thermodynamically favored homochiral cages, can be controlled through specific anion encapsulation. Non-encapsulating anion afforded a mixture of all possible diastereomers. Anion exchange enabled structural transformations between the diastereomers and the conversion of the mixture of diastereomers into homochiral diastereomers.