Guest-induced supramolecular isomerism in inclusion complexes of T-shaped host 4,4-bis(4'-hydroxyphenyl)cyclohexanone

The T-shaped host molecule 4,4-bis(4'-hydroxyphenyl)cyclohexanone (1) has an equatorial phenol group and a cyclohexanone group along the arms and an axial phenol ring as the stem. The equatorial phenyl ring adopts a "shut" or "open" conformation, like a windowpane, depending on the size of the guest (phenol or o/m-cresol), for the rectangular voids of the hydrogen-bonded ladder host framework. The adaptable cavity of host 1 expands to 11x15-18 A through the inclusion of water with the larger cresol and halophenol guests (o-cresol, m-cresol, o-chlorophenol, and m-bromophenol) compared with a size of 10x13 A for phenol and aniline inclusion. The ladder host framework of 1 is chiral (P2(1)) with phenol, whereas the inclusion of isosteric o- and m-fluorophenol results in a novel polar brick-wall assembly (7x11 A voids) as a result of auxiliary C-H...F interactions. The conformational flexibility of strong O-H...O hydrogen-bonding groups (host 1, phenol guest), the role of guest size (phenol versus cresol), and weak but specific intermolecular interactions (herringbone T-motif, C-H...F interactions) drive the crystallization of T-host 1 towards 1D ladder and 2D brick-wall structures, that is, supramolecular isomerism. Host 1 exhibits selectivity for the inclusion of aniline in preference to phenol as confirmed by X-ray diffraction, 1H NMR spectroscopy, and thermogravimetry-infrared (TG-IR) analysis. The T(onset) value (140 degrees C) of aniline in the TGA is higher than those of phenol and the higher-boiling cresol guests (T(onset)=90-110 degrees C) because the former structure has more O-H...N/N-H...O hydrogen bonds than the clathrate of 1 with phenol which has O-H...O hydrogen bonds. Guest-binding selectivity for same-sized phenol/aniline molecules as a result of differences in hydrogen-bonding motifs is a notable property of host 1. Host-guest clathrates of 1 provide an example of spontaneous chirality evolution during crystallization and a two-in-one host-guest crystal (phenol and aniline), and show how weak C-H...F interactions (o- and m-fluorophenol) can change the molecular arrangement in strongly hydrogen-bonded crystal structures.     

Guest-dependent flexible coordination networks with fluorinated ligands

Guest-dependent flexible coordination networks are formed from 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf), 4,4'-bis(4-pyridylmethyl)octafluorobiphenyl (bpfb), 2,6-bis(4-pyridylmethyl)hexafluoronaphthalene (2,6-bpfn), and 2,7-bis(4-pyridylmethyl)hexafluoronaphthalene (2,7-bpfn) with Cd(NO3)2 in the presence of various organic compounds. The reaction of bpf affords one-dimensional cyclic chains, two-dimensional rhombus grid sheets, and three-dimensional diamond frameworks with threefold interpenetration. The reaction of bpfb mainly affords two-dimensional rhombus grid sheets with twofold parallel interpenetration. The reaction of 2,6-bpfn affords a one-dimensional ladder and two-dimensional rhombus grid, twisted grid, and herringbone sheets. The reaction of 2,7-bpfn affords two-dimensional rhombus grid sheets and grid sheets with dumbbell-shaped cavities. This diversity of network topologies is induced by interactions between the guest molecules and the flexible ligand frameworks.     

Guanidinium binding modulates guest exchange within an [M4L6] capsule

Take it slow! A metal-organic container molecule has been shown to bind guanidinium cations (blue) between the sulfonate groups on its periphery, as well as accommodating guests such as cyclopentane and cyclohexane in its internal cavity (red). Kinetic studies on the system demonstrated a linear relationship between the amount of bound guanidinium ions and the rate of guest exchange.     

An extremely stable host-guest complex that functions as a fluorescence probe for calcium ions

Herein, we report a crown ether based molecular cage that forms extremely stable supramolecular complexes with dimethyldiazapyrenium (DMDAP) ions in CD(3)CN through the collaboration of multiple weak C-HO hydrogen bonds. The very strong binding affinity in this host-guest system allows the molecular cage to bleach the fluorescence signal of DMDAP substantially in equimolar solutions at concentrations as low as 1 x 10(-5) M. Remarkably, a 1x10(-5) M equimolar solution of the molecular cage and DMDAP is highly selective toward Ca(2+) ions-relative to other biologically important Li(+), Na(+), K(+), and Mg(2+) ions-and causes a substantial increase in the fluorescence intensity of the solution. As a result, this molecular cage/DMDAP complex behaves as a supramolecular fluorescence probe for the detection of Ca(2+) ions in solution.     

Efficient synthesis of calix[6]tmpa: a new calix[6]azacryptand with unique conformational and host-guest properties

A new C(3v)-symmetrical calix[6]azacryptand, that is, calix[6]tmpa (11), was synthesized by efficient [1+1] macrocyclization reactions. Remarkably, both linear and convergent synthetic strategies that were applied lead to equally good overall yields. Calix[6]tmpa behaves as a single proton sponge and appeared reluctant to undergo polyprotonation, unlike classical tris(2-pyridylmethyl)amine (tmpa) derivatives. It also acts as a good host for ammonium ions. Interestingly, it strongly binds a sodium ion and a neutral guest molecule, such as a urea, an amide, or an alcohol, in a cooperative way. A (1)H NMR study indicated that the ligand, as well as its complexes, adopt a major flattened cone conformation that is the opposite of that observed with the previously reported calix[6]cryptands. Characterization of the monoprotonated derivative 11H(+) by X-ray diffraction also revealed the presence of a 1,3-alternate conformation, which is the first example of its kind in the calix[6]arene family. This conformer is probably also present in solution as a minor species. The important covalent constraint induced by the polyaromatic tmpa cap on the calixarene skeleton, and conversely from the calix core onto the tmpa moiety, is the likely basis for the unique conformational and chemical properties of this host.     

Putting anion-π interactions into perspective

Supramolecular chemistry is a field of scientific exploration that probes the relationship between molecular structure and function. It is the chemistry of the noncovalent bond, which forms the basis of highly specific recognition, transport, and regulation events that actuate biological processes. The classic design principles of supramolecular chemistry include strong, directional interactions like hydrogen bonding, halogen bonding, and cation-π complexation, as well as less directional forces like ion pairing, π-π, solvophobic, and van der Waals potentials. In recent years, the anion-π interaction (an attractive force between an electron-deficient aromatic π system and an anion) has been recognized as a hitherto unexplored noncovalent bond, the nature of which has been interpreted through both experimental and theoretical investigations. The design of selective anion receptors and channels based on this interaction represent important advances in the field of supramolecular chemistry. The objectives of this Review are 1) to discuss current thinking on the nature of this interaction, 2) to survey key experimental work in which anion-π bonding is demonstrated, and 3) to provide insights into the directional nature of anion-π contact in X-ray crystal structures.