Self-Assembly of Rhenium(I) Double-Stranded Helicate and Mesocate from Flexible Ditopic Benzimidazolyl/Naphthanoimidazolyl N-Donor and Rigid Bis-Chelating Hydroxyphenylbenzimidazolyl N∩OH-Donor Ligands: Synthesis, Characterization, and Photophysical and B-DNA Docking Studies.

The self-assembly of three rheniumtricarbonyl core-based supramolecular coordination complexes (SCCs), fac-[Re(CO)3(µ-L)(µ-L')Re(CO)3] (1-3) was carried out using Re2(CO)10, rigid bis-chelating ligand (HO∩N-Ph-N∩OH (L1) (where HO∩N = 2-hydroxyphenylbenzimidazolyl), and flexible ditopic N-donor ligands (L2 = bis(3-((1H-benzoimidazol-1-yl)methyl)-2,4,6-trimethylphenyl)methane, L3 = bis(3-((1H-naphtho[2,3-d]imidazol-1-yl)methyl)-2,4,6-trimethylphenyl)methane, L4 = bis(4-(naphtho[2,3-d]imidazol-1-yl-methyl)phenyl)methane) via a one-pot solvothermal approach. In the solid state, the dinuclear SCCs adopt heteroleptic double-stranded helicate and meso-helicate architectures. The supramolecular structures of the complexes are retained in the solution based on the 1H NMR and electrospray ionization (ESI)-mass analysis. The spectral and photophysical properties of the complexes were studied both experimentally and using time-dependent density functional theory (TDDFT) calculations. All of the supramolecules exhibited emission in both solution and solid states. Theoretical studies were conducted to determine the chemical reactivity parameters, molecular electrostatic potential surface plots, natural population, and Hirshfeld analysis for complexes 1-3. Additionally, molecular docking studies were carried out for complexes 1-3 with B-DNA.

Rhenium(I)-Based Heteroleptic Pentagonal Toroid-Shaped Metallocavitands: Self-Assembly and Molecular Recognition Studies.

A family of neutral, heteroleptic, dinuclear M2LL'-type pentagonal toroid-shaped metallomacrocycles (1-8) were synthesized using flexible ditopic N donors (Ln = L1-L2), rigid bis-chelating ligands (H2-L' = H2-E), and Re2(CO)10 in a one-pot solvothermal self-assembly approach. The ligands and the metallomacrocycles were characterized using ATR-IR, electrospray ionization mass spectrometry, nuclear magnetic resonance, ultraviolet-visible, and emission spectroscopy methods. The molecular structures of 1, 2, 4, 6, and 7 were confirmed by an X-ray diffraction study and are similar to those of calix[5]arene. The cyclic inner cavities of the metallomacrocycles accommodate toluene/mesitylene/acetone/chlorobenzene as guest molecules that are stabilized by cumulative C-H···π and π···π interactions with the cyclic framework of metallomacrocycle. The photophysical properties of the ligands and the metallomacrocycles were studied. The host-guest recognition properties of metallocavitands 1, 2, 7, and 8 as a model host with phenol and nitrobenzene derivatives as guest molecules were studied by emission spectroscopy methods.

Calix[4]arene-Analogous Technetium Supramolecules.

Calix[4]arene-analogous technetium supramolecules (1 and 2) were assembled using (NBu4)[Tc2(µ-Cl)3(CO)6] and neutral flexible bidentate nitrogen-donor ligands (L1 and L2) consisting of four arene units covalently joined via methylene units. The neutral homoleptic technetium macrocycles adopt a partial cone/cone-shaped conformation in the solid state. These supramolecules are the first example of fac-[Tc(CO)3]+ core-based metallocalix[4]arenes and second example of fac-[Tc(CO)3]+ core-based metallomacrocycles. Structurally similar fac-[Re(CO)3]+ core-based macrocycles (3 and 4) were also prepared using [Re(CO)5X] (where X = Cl or Br) and L1 or L2. The products were characterized spectroscopically and by X-ray analysis.

Emerging Spacers-Based Ligands for Supramolecular Coordination Complexes.

The design and self-assembly of supramolecular coordination complexes (SCCs) i. e., discrete cyclic metalloarchitectures such as cycles, cages, mesocates, and helicates with desired size, shape, and properties have been increasing exponentially owing to their potential applications in molecular sensors, molecular cargos, molecular recognition, and catalysis. The introduction of the organic motifs and metal complexes as a spacer provides functionality to the metalloarchitecture. This review mainly focusses on newly evolving spacer based ligands employed to yield simple to high-order metallosupramolecular assemblies using straight-forward approaches. The new spacers including corannulene, organic cyclic framework, bicyclic organic motifs, aliphatic chain, metalloligands, triarylboron, BODIPY, azaphosphatrane, phosphine, and thio/selenophosphates offer a great set of properties and in-built functionalities to the metalloarchitectures which are discussed in this review.

Rhenium(i) based irregular pentagonal-shaped metallacavitands.

Neutral ditopic flexible N-donor ligands (Ln = bis(4-(naphtho[2,3-d]imidazol-1-ylmethyl)phenyl)methane, L1 bis(4-(benzimidazol-1-ylmethyl)phenyl)methane, L2 or bis(4-(2-nonylbenzimidazol-1-ylmethyl)phenyl)methane, L3) possessing a bis(4-methylphenyl)methane spacer with two imidazolyl donor units were designed and synthesized. The ligands were utilized to develop metallacavitands analogous to irregular pentagonal-shaped metallacavitands with larger cavities. The metallacavitands 1-4 were assembled from Re2(CO)10, a rigid bis-chelating donor (1,4-dihydroxy-9,10-anthraquinone or chloranilic acid) and Lnvia a solvothermal approach. The ligands and the metallacavitands were characterized by analytical and spectroscopic methods. The molecular structures of 1 and 4 were further confirmed by single crystal X-ray diffraction analysis which revealed that a toluene molecule resides in the hydrophobic cavity. Ln and 1-4 are emissive in DMSO at room temperature. The internal cavity of the metallacavitand acts as a host for aromatic guest molecules. The host-guest interaction properties of 1 with anthracene, naphthalene, nitrobenzene, 2-nitrotoluene, 4-nitrotoluene and 2,4-dinitrotoluene were studied by an emission spectroscopic method.