A Self-Assembled Electro-Active M8L4 Cage Based on Tetrathiafulvalene Ligands.

Two self-assembled redox-active cages are presented. They are obtained by coordination-driven self-assembly of a tetra-pyridile tetrathiafulvalene ligand with cis-M(dppf)(OTf)₂ (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both species are fully characterized and are constituted of 12 electro-active subunits that can be reversibly oxidized.

Biomedical and biochemical applications of self-assembled metallacycles and metallacages.

Metal ions and metal complexes with organic molecules are ubiquitous in nature. Bulk metal ions of Na, K, Mg, and Ca constitute as much as 1% of human body weight. The remaining trace ions, most commonly of Fe, Ni, Cu, Mn, Zn, Co, Mo, and V, make up ∼0.

Growth Inhibitory Activity of a Bis-benzimidazole-Bridged Arene Ruthenium Metalla-Rectangle and Prism.

Two new supramolecular coordination complexes (SCCs), were obtained from the self-assembly of a new bis-benzimidazole bridged Ru acceptor, , with dipyridyl and tripyridyl donors, respectively. As part of a growing library of anticancer-active Ru-based SCCs, metalla-prism selectively showed high cytotoxicities relative to cisplatin for a series of cancer cell lines, with IC values as low as 8.41 μM for MCF7 cells, as determined from MTS assays.

Self-assembly of ambidentate pyridyl-carboxylate ligands with octahedral ruthenium metal centers: self-selection for a single-linkage isomer and anticancer-potency studies.

The synthesis of six new [2+2] metallarectangles through the coordination-driven self-assembly of octahedral Ru(II)-based acceptors with ambidentate pyridyl-carboxylate donors is described. These molecular rectangles are fully characterized by (1)H NMR spectroscopy, high-resolution electrospray mass spectrometry, and single-crystal X-ray diffraction. In each case, despite the possible formation of multiple isomers, based on the relative orientation of the pyridyl and carboxylate groups (head-to-head versus head-to-tail), evidence for the formation of a single preferred ensemble (head-to-tail) was found in the (1)H NMR spectra.

Self-assembled metalla-rectangles bearing azodipyridyl ligands: synthesis, characterization and antitumor activity.

Sixteen arene-Ru based molecular-rectangles were self-assembled in high yields by the equimolar mixing of arene-Ru acceptors (Aa-Ad) with various azopyridyl ligands (1,2-di(pyridyl-4yl)diazene (L1), 1,2-bis(pyridin-4-ylmethylene)hydrazine (L2), 1,2-bis(1-(pyridin-4-yl)ethylidene)hydrazine (L3), 1,2-bis(pyridin-4-ylmethylene)hydrazine (L4)) in nitromethane-methanol solutions. These new molecular-rectangles were fully characterized by a host of analytical techniques including elemental analysis, (1)H and (13)C NMR and HR-ESI-MS. The solid-state structures of two molecular-rectangles (1b and 4d) were determined by single crystal X-ray diffraction data.

Coordination-driven self-assembly of 2D-metallamacrocycles using a new carbazole-based dipyridyl donor: synthesis, characterization, and C60 binding study.

A new carbazole-based 90° dipyridyl donor 3,6-di(4-pyridylethynyl)carbazole (L) containing carbazole-ethynyl functionality is synthesized in reasonable yield using the Sonagashira coupling reaction. Multinuclear NMR, electrospray ionization-mass spectrometry (ESI-MS), including single crystal X-ray diffraction analysis characterized this 90° building unit. The stoichiometry combination of L with several Pd(II)/Pt(II)-based 90° acceptors (1a-1d) yielded [2 + 2] self-assembled metallacycles (2a-2d) under mild conditions in quantitative yields [1a = cis-(dppf)Pd(OTf)(2); 1b = cis-(dppf)Pt(OTf)(2); 1c = cis-(tmen)Pd(NO(3))(2); 1d = 3,6-bis{trans-Pt(C≡C)(PEt(3))(2)(NO(3))}carbazole].

Coordination-driven self-assembly of ruthenium-based molecular-rectangles: synthesis, characterization, photo-physical and anticancer potency studies.

A suite of eight cationic, tetra-metallic molecular rectangles (1-8) was generated via coordination-driven self-assembly using four dicarboxylate-bridged arene-Ru precursors (A1-A4) with one of two dipyridyl ligands (D1, D2). The high-yielding (84-92%) rectangles were characterized by (1)H NMR and HR-ESI-MS to support their structural assignments. The molecular structure of 5 was determined by single crystal X-ray analysis, which indicated that two D2 ligands bridge two A1 acceptors to form a rectangular construct.

Self-assembly of Cationic, Hetero- or Homo-nuclear Ru(II) Macrocyclic Rectangles and their Photophysical, Electrochemical and Biological Studies.

A series of supramolecular rectangles, including two mixed-metal Ru/Pt complexes, have been formed by the coordination-driven self-assembly of a range of arene-Ru "molecular clip" acceptors (1a-1d) with rigid dipyridyl-based ligands (2a-2d) over the course of 10 hours in solution. The isolated products were characterized by multinuclear NMR ((1)H and (13)C or (31)P), HR-ESI-MS and an X-ray diffraction study to support the ascribed two-component rectangular structures. The rectangles were further characterized by UV-Vis and fluorescence studies.

DNA binding and unwinding by self-assembled supramolecular hetero-bimetallacycles.

Two new tetracationic hetero-bimetallacycles were prepared from a bis-pyridine amide ligand and metal (Pd and Pt) acceptors. We found that both self-assembled hetero-bimetallacycles bind and unwind supercoiled DNA as established by photophysical and gel electrophoresis analyses, respectively.

Self-assembled metalla-bowls for selective sensing of multi-carboxylate anions.

Two new tetranuclear cationic metalla-bowls 4 and 5 were self-assembled from a bis-pyridine amide ligand (H(2)L) (1) and arene-ruthenium acceptors, [(Ru(2)(μ-η(4)-C(2)O(4))(η(6)-p-cymene)(2)](O(3)SCF(3))(2) (2) and [Ru(2)(dhnd)(η(6)-p-cymene)(2)](O(3)SCF(3))(2) (dhnd = 6,11-dihydroxy-5,12-naphthacenedionato) (3), respectively. The metalla-bowls were characterized by multinuclear NMR, ESI-MS, UV-Vis spectroscopy, and single crystal X-ray diffraction study of 4. The crystal structure of 4 reveals unambiguous proof for the molecular shape of the metalla-bowl and the encapsulation of one triflate anion in the cavity through hydrogen bonding.

A unique non-catenane interlocked self-assembled supramolecular architecture and its photophysical properties.

A novel, interlocked, self-assembled (M(2)L(2))(2) molecular architecture was constructed from an arene-Ru acceptor and a 1,4-di(pyridin-4-yl)buta-1,3-diyne donor. Two M(2)L(2) units, with cavities of ~7.21 Å, spontaneously interlock, with one unit encapsulating a twin in a non-catenane fashion.

Coordination Driven Self-Assembly and Anticancer Activity of Molecular Rectangles Containing Octahedral Ruthenium Metal Centers.

The synthesis of new 2+2 metalla-rectangles via coordination driven self-assembly of octahedral Ru(II) based acceptors and amide donors is described. To evaluate their in vitro cytotoxic properties, preliminary biological assays were carried out for various human cancer cell lines, and our results show that the cytotoxicity level of 3 is comparable or even greater in the cases of SK-hep-1 and HCT-15 than that of the reference drug cisplatin.

Self-assembled arene-ruthenium-based rectangles for the selective sensing of multi-carboxylate anions.

Novel arene-ruthenium [2+2] metalla-rectangles 4 and 5 have been synthesized by self-assembly using dipyridyl amide ligand 3 and arene-ruthenium acceptors (arene: benzoquinone (1), naphthacenedione (2)) and characterized by NMR spectroscopy and ESI-MS. The solid-state structure of 5 was determined by X-ray diffraction and shows encapsulated diethyl ether molecule in the rectangular cavity of 5. The luminescent 5 was further used for anion sensing with the amidic linkage serving as a hydrogen-bond donor site for anions and the ruthenium moiety serving as a signaling unit.

Hexanuclear self-assembled arene-ruthenium nano-prismatic cages: potential anticancer agents.

Two novel nano-cage compounds, 8 and 9, were prepared by self-assembly of the ruthenium complexes 4 and 5, and the tripodal donor 1. The cytotoxicity of 8 was found to be considerably stronger than that of cisplatin. The complex 8 inhibited tumor cell proliferation by interfering into regulatory pathways of the cell cycle via apoptosis.

Self-assembled molecular squares containing metal-based donor: synthesis and application in the sensing of nitro-aromatics.

Self-assemblies between a linear Pt-based donor and ferrocene- chelated metallic acceptors produced novel heterometallic squares 4 and 5, which show fluorescence quenching upon the addition of nitro-aromatics.

Coordination-driven self-assembly of M3L2 trigonal cages from preorganized metalloligands incorporating octahedral metal centers and fluorescent detection of nitroaromatics.

The design and preparation of novel M(3)L(2) trigonal cages via the coordination-driven self-assembly of preorganized metalloligands containing octahedral aluminum(III), gallium(III), or ruthenium(II) centers is described. When tritopic or dinuclear linear metalloligands and appropriate complementary subunits are employed, M(3)L(2) trigonal-bipyramidal and trigonal-prismatic cages are self-assembled under mild conditions. These three-dimensional cages were characterized with multinuclear NMR spectroscopy ((1)H and (31)P) and high-resolution electrospray ionization mass spectrometry.