Site-selective quantum correlations revealed by magnetic anisotropy in the tetramer system SeCuO3

We present the investigation of a monoclinic compound SeCuO3 using x-ray powder diffraction, magnetization, torque and electron-spin-resonance (ESR). Structurally based analysis suggests that SeCuO3 can be considered as a 3D network of tetramers. The values of intra-tetramer exchange interactions are extracted from the temperature dependence of the susceptibility and amount to ~200 K. The inter-tetramer coupling leads to the development of long-range antiferromagnetic order at TN = 8 K. An unusual temperature dependence of the effective g-tensors is observed, accompanied with a rotation of macroscopic magnetic axes. We explain this unique observation as due to site-selective quantum correlations

Exploitation of the Menshutkin reaction for the controlled assembly of halogen bonded architectures incorporating 1,2-diiodotetrafluorobenzene and 1,3,5-triiodotrifluorobenzene

1,4-Diazabicyclo[2.2.2]octane (DABCO) forms well-defined co-crystals with 1,2-diiodotetrafluorobenzene (1,2-DITFB), [(1,2-DITFB) DABCO], and 1,3,5-triiodotrifluorobenzene, [(1,3,5-TITFB) DABCO]. Both systems exhibited lowerthan-expected supramolecular connectivity, which inspired a search for polymorphs in alternative crystallization solvents. In dichloromethane solution, the Menshutkin reaction was found to occur, generating chloride anions and quaternary ammonium cations through the reaction between the solvent and DABCO. The controlled in situ production of chloride ions facilitated the crystallization of new halogen bonded networks, DABCO-CH Cl[(1,2-DITFB)Cl] (zigzag X-bonded chains) and (DABCO-CH Cl) [(1,3,5-TITFB) Cl ] ·CHCl3 (2D pseudo-trigonal X-bonded nets displaying Borremean entanglement), propagating with charge-Assisted C-I⋯Cl-halogen bonds. The method was found to be versatile, and substitution of DABCO with triethylamine (TEA) gave (TEA-CH Cl) [(1,2-DITFB)Cl ] ·4(H O) (mixed halogen bond hydrogen bond network with 2D supramolecular connectivity) and TEA-CH Cl[(1,3,5-TITFB)Cl] (tightly packed planar trigonal nets). The co-crystals were typically produced in high yield and purity with relatively predictable supramolecular topology, particularly with respect to the connectivity of the iodobenzene molecules. The potential to use this synthetic methodology for crystal engineering of halogen bonded architectures is demonstrated and discussed

Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

Halogen bonding (XB), the attractive interaction between an electron-deficient halogen atom and a Lewis base, has undergone a dramatic development as an intermolecular force analogous to hydrogen bonding (HB). However, its utilization in the solution phase remains underdeveloped. Furthermore, the design of receptors capable of strong and selective recognition of anions in water remains a significant challenge. Here we demonstrate the superiority of halogen bonding over hydrogen bonding for strong anion binding in water, to the extent that halide recognition by a simple acyclic mono-charged receptor is achievable. Quantification of iodide binding by rotaxane hosts reveals the strong binding by the XB-rotaxane is driven exclusively by favourable enthalpic contributions arising from the halogen-bonding interactions, whereas weaker association with the HB-rotaxanes is entropically driven. These observations demonstrate the unique nature of halogen bonding in water as a strong alternative interaction to the ubiquitous hydrogen bonding in molecular recognition and assembly