: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

The nature and characteristics of the CH/π interaction are discussed by comparison with other weak molecular forces such as the CH/O and OH/π interaction. The CH/π interaction is a kind of hydrogen bond operating between a soft acid CH and a soft base π-system (double and triple bonds, C6 and C5 aromatic rings, heteroaromatics, convex surfaces of fullerenes and nanotubes). The consequences of CH/π hydrogen bonds in supramolecular chemistry are reviewed on grounds of recent crystallographic findings and database analyses. The topics include intramolecular interactions, crystal packing (organic and organometallic compounds), host/guest complexes (cavity-type inclusion compounds of cyclodextrins and synthetic macrocyclic hosts such as calixarenes, catenanes, rotaxanes and pseudorotaxanes), lattice-inclusion type clathrates (including liquid crystals, porphyrin derivatives, cyclopentadienyl compounds and C60 fullerenes), enantioselective clathrate formation, catalytic enantioface discriminating reactions and solid-state photoreaction. The implications of the CH/π concept for crystal engineering and drug design are evident.

CH/π hydrogen bonds in crystals

Calixarenes are macrocyclic molecules, like crown ethers and cyclodextrins.1-7 Calixarenes made up of phenol and methylene units have many conformational isomers because of two possible rotational modes of the phenol unit: the oxygen-through-theannulus rotation and the para-substituent-throughthe-annulus rotation (Figure 1). The conformational isomers thus yielded afford a great number of unique cavities with the different size and the different shape. Recently, a number of strategies have been exploited by which not only the conformation of calix[4]arenes, but also those of calix[6]arenes and calix[8]arenes, can be immobilized. This means that our group can now design various calixarene-based receptors that show high selectivity for guest molecules and metal cations. In this review article, our group describe novel strategies for cavity design using calix[n]arene skeletons, strategies that are intended to allow complexation of specific molecular targets or metal ions.

Novel Cavity Design Using Calix[n]arene Skeletons: Toward Molecular Recognition and Metal Binding.

Manufactured nanoparticles: An overview of their chemistry, interactions and potential environmental implications

Spontaneous self-assembly processes that lead to discretespherical molecular structures are common in nature. Sphericalviruses1 (such ashepatitis B) and fullerenes2 are well-known examples inwhich non-covalent and covalent forces,respectively, direct the assembly of smaller subunits intolarger superstructures. A common feature of theseshell-like architectures is their ability to encapsulateneutral and/or charged guests whose size, shape and chemicalexteriors complement those of the host's innersurface3,4. Their interiors can often beregarded as a new phase of matter5, capable of controlling the flowof reactants, transients and products, and of catalysingreactions of both chemical and biological relevance. Suchproperties have inspired the recent emergence ofmonomolecular5,6,7 and supramolecular dimeric molecularcapsules8,9, many of which have been basedon the head-to-head alignment of bowl-shapedpolyaromatic macrocycles such as calix[4]arenes5,7,9. But true structural mimicry offrameworks akin to viruses and fullerenes, which are based onthe self-assembly of n > 3 subunits,and where surface curvature is supplied by edge sharing of regularpolygons, has remained elusive. Here we present anexample of such a system: a chiral spherical molecular assemblyheld together by 60 hydrogen bonds (1) (Fig. 1). We demonstrate the ability of 1, which consists of six calix[4]resorcinarenes 2 and eight water molecules, to self-assemble and maintain its structure in apolar media and to encapsulate guest species within a well-defined cavity that possesses an internal volume of about 1,375 A3. Single crystal X-ray analysis shows that its topology resembles that of a spherical virus1 and conforms to the structure of a snub cube, one of the 13 Archimedean solids10.

A chiral spherical molecular assembly held together by 60 hydrogen bonds

MOLECULAR complexation of fullerenes in host–guest complexes has the potential to afford efficient large-scale purification of fullerenes1. This method would avoid the losses inherent in the chromatographic techniques currently in use, which arise from irreversible absorption on the stationary phase2. Several host-guest interactions have been reported for C60, including the formation of complexes with 1,4-hydroquinone3,4, azacrown compounds5, certain water-soluble macrocycles such as γ-cyclodextrin6–8, and complexation between C60 and an iridium phosphine in which pendant groups attached to a phosphorus atom form a cradle for an adjacent C60 molecule9. Other relevant studies are the inclusion of C60 into a microporous aluminophosphate10 and the formation of a charge-transfer complex between C60 and a thiafulvalene11. Here we show that both C60 and C70 will form discrete complexes with calixarenes, bowl-shaped macrocycles with hydrophobic cavities. Complexation of p-Bu'-calix[8]arene with a mixture of the toluene extract of 'crude' fullerene soot, followed by a series of recrystallizations, affords >99.5% pure C6. Our approach could lead to a substantial reduction in the cost of purifying C60 and C70.

Purification of C60 and C70 by selective complexation with calixarenes

Lewis base adducts of alane and gallane

Bending in molecular crystals is typically associated with the anisotropy of intermolecular interactions. The intriguing observation is reported of plastic bending in dimethyl sulfone, which exhibits nearly isotropic crystal packing and interaction topology, defying the known structural models of bending crystals. The origin of the bending phenomenon has been explored in terms of intermolecular interaction energies, experimental X-ray charge density analysis, and variable temperature neutron diffraction studies. H⋅⋅⋅H dihydrogen interactions and differences in electrostatic complementarity between molecular layers are found to facilitate the bending behavior.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201701972

The Elusive Structural Origin of Plastic Bending in Dimethyl Sulfone Crystals with Quasi-isotropic Crystal Packing.

Extension of previous work on the lanthanide(III) ion complexes of p-tert-butyltetrathiacalix[4]arene has led to a variety of structurally characterised species containing oxo-, hydroxo- and aqua-ligands presumably derived from water present in the preparative medium, along with the thiacalixarene in various stages of deprotonation. The overall stoichiometry of some species is remarkably complicated due to the presence of simple anions and multiple solvents. Simplest is the binuclear complex [(μ-H2O){Ln(O-dmf)2}2(HL·dmf)2]·nS (dmf = dimethylformamide) [1Ln, Ln = Sm (nS = 2dmf), Eu (nS = 1.5dmf·2MeCN)], also the best-defined of all the arrays studied. The heaviest lanthanides give trinuclear Ln(OH)3·2Ln(LH)·xdmf·yH2O (2Ln, Ln = Yb, Lu), while both oxo and hydroxo species are isolable with Eu: trinuclear Eu3O(L)(LH)(LH4)·13dmf (3) and tetranuclear Eu4O(OH)2(L)(LH2)2(LH4)·12dmf (9), both somewhat atypical species containing uncoordinated thiacalixarene molecules within the lattice. Anion (NO3, ClO4) coordination, as in the tri- and tetranuclear species, 4–6Ln, 9, 10Ln, 11Ln, 12, seems especially favoured for the lighter lanthanides. In these arrays, the Ln3 and Ln4 aggregates are triangular or (quasi-)square-planar, except for Gd4O2(LH2)4·2H2O·2MeOH·2dmf·3.375CH2Cl2 (12), where there is a Z-disposition. Most common is an Ln3O core, which spans the gamut of Ln in three sets of crystal forms with cells of similar dimensions: for Ln = La...Nd, Ln3(OH)(NO3)4(LH2)2·4.5dmf (5Ln) (space group C2/m), and Sm...Lu, Ln3O(NO3)(LH)2·4H2O·2dmso·2MeCN·3py (6Ln) (space group P21/n), conformity with crystallographic symmetryentails disorder of the Ln atoms; in a further form of lowersymmetry Pn, (pyH)Ln3O(NO3)2(LH)2·2MeCN·xH2O·ydmso·1.5py·MeOH (7Ln, Ln = La, Ce), with no imposed crystallographic symmetry, some disorder persists, but none is found in the crystallographically unrelated form of 8Pr, Pr3O(NO3)(LH)2·16H2O·2MeCN·5py. Ln4(OH)(NO3)3(L)2·8dmf·2dmso·3H2O (10Ln, Ln = Pr...Gd, previously defined for Nd) has a square-planar Ln4O array sandwiched between a pair of L ligands, with a similar form found for Ln4O(ClO4)2(L2)·xdmf·yH2O (11Ln, Ln = La...Nd).

George A. Koutsantonis

Papers

Purification of C60 and C70 by selective complexation with calixarenes

Lewis base adducts of alane and gallane

The Elusive Structural Origin of Plastic Bending in Dimethyl Sulfone Crystals with Quasi-isotropic Crystal Packing.

Systematic Structural Coordination Chemistry of p-tert-Butyltetrathiacalix[4]arene: Further Complexes of Transition-Metal Ions†

Koilands from thiophiles: mercury(II) clusters from thiacalixarenes