Binding of organic guests containing acidic or basic groups inside a water-soluble coordination cage host shows strong pH dependence.

The Kemp elimination (reaction of benzisoxazole with base to give 2-cyanophenolate) is catalyzed in the cavity a cubic M8L12 coordination cage because combination (i) binding driven by hydrophobic effect, and (ii) accumulation hydroxide ions around 16+ surface ion-pairing. Here we show how reaction cavity-bound guest modified presence other anions which can also accumulate displace hydroxide, inhibiting catalysis cage-based reaction. Addition chloride or fluoride inhibits extent that new...

Size and shape criteria for guest binding inside the cavity of an octanuclear cubic coordination cage in water have been established using a new fluorescence displacement assay to quantify binding. For aliphatic cyclic ketones increasing size (from C5 C11), there is linear relationship between ΔG guest's surface area: change 0.3 kJ mol–1 Å–2, corresponding 5 each additional CH2 group guest, good agreement with expectations based on hydrophobic desolvation. The highest association constant K...

Abstract Unusual demethylenation reactions of cyclopropanes under UV‐light irradiation were found within a cavity photoactive coordination cage. The reaction proceeded via guest‐to‐host electron transfer owing to the highly electron‐deficient nature chemoselective and enabled late‐stage derivatization steroid molecule, which led totally new un‐natural steroid.

The self-assembly between a water-soluble bis-bidentate ligand L18w and Co(II) salts in water affords three high-spin products: dinuclear meso-helicate [Co2(L18w)3]X4; tetrahedral cage [Co4(L18w)6]X8; dodecanuclear truncated-tetrahedral [Co12(L18w)18]X24 (X = BF4 or ClO4). All products were crystallized under different conditions structurally characterized. In [Co2(L18w)3]X4 all bridging ligands span pair of metal ions; the two larger products, there is ion at each vertex Co4 Co12 polyhedral...

Abstract The cavity of an M 8 L 12 cubic coordination cage can accommodate a cluster ten water molecules in which the average number hydrogen bonds per molecule is 0.5 H‐bonds less than it would be bulk solution. presence these “hydrogen‐bond frustrated” or “high‐energy” results hydrophobic effect associated with guest binding being predominantly enthalpy‐based, as improve their hydrogen‐bonding environment on release. This contrasts classical form favourable entropy change release ordered...

The protein/ligand docking programme ‘GOLD’ can be used to identify new strongly-binding guests for a synthetic coordination cage host.

We have prepared a series of mononuclear fac and mer isomers Ru(II) complexes containing chelating pyrazolyl-pyridine ligands, to examine their differing ability act as hydrogen-bond donors in MeCN. This was prompted by our earlier observation that octanuclear cube-like coordination cages contain these types metal vertex can bind guests such isoquinoline-N-oxide (K = 2100 M(-1) MeCN), with significant contribution binding being hydrogen-bonding interaction between the electron-rich atom...

We demonstrate the use of a simple pH swing to control selection one three different guests from aqueous solution by coordination cage host.

We have performed a systematic investigation of the effects guest flexibility on their ability to bind in cavity coordination cage host water, using two sets isomeric aliphatic ketones that differ only branching patterns alkyl chains. Apart from expected increase binding strength for C

Abstract Unusual demethylenation reactions of cyclopropanes under UV‐light irradiation were found within a cavity photoactive coordination cage. The reaction proceeded via guest‐to‐host electron transfer owing to the highly electron‐deficient nature chemoselective and enabled late‐stage derivatization steroid molecule, which led totally new un‐natural steroid.

Abstract The interaction with duplex DNA of a small library structurally related complexes that all contain d 6 ‐metal ion coordinated to either the 2,2 ′ :4,4 ′′ :4 ,4 ′′′ ‐quaterpyridyl ligand or its methylated derivative are reported. This is made up mixture newly synthesised and previously reported systems. Despite their structural similarities display an almost 20‐fold variation in binding affinities. Although effects due overall charge apparent, differences characteristics deeper than...

Stepwise preparation of the heterometallic octanuclear coordination cages [(M(a))4(M(b))4L12](16+) is reported, in which M(a) = Ru or Os and M(b) Cd Co (all their +2 oxidation state). This requires initial kinetically inert mononuclear complexes [(M(a))L3](2+) L a ditopic ligand with two bidentate chelating pyrazolyl-pyridine units: one terminus each bound to metal ion, such that complex has three pendant sites at cage assembly can propagate by additional labile ions separate step. Thus,...

A cubic coordination cage shows high selectivity for CO₂<italic>vs.</italic> N₂ uptake in the cavity, despite bulk material being non-porous.

To investigate how remotely induced changes in ligand folding might affect catalysis by organometallic complexes, dynamic α-amino-iso-butyric acid (Aib) peptide foldamers bearing rhodium(I) N-heterocyclic carbene (NHC) complexes have been synthesized and studied. X-ray crystallography of a foldamer with an N-terminal azide C-terminal Rh(NHC)(Cl)(diene) complex showed racemate chiral axis the Rh(NHC) distorted 310 helical body. Replacing either one or two L-α-methylvaline (L-αMeVal) residues...

Abstract Invited for the cover of this issue is group Michael D. Ward at Universities Warwick and Sheffield. The image depicts ‘hydrophobic effect’ that responsible guest binding in host cavity. Read full text article 10.1002/chem.201704163 .