Metal Template Synthesis of ‘Broken’ Aromatic Preorganized Terdentate Hosts for the Recognition of Lanthanide Tris-β-Diketonate Guests

The binding of the terdentate precursor 2,2′-(4-methyl-3,5-divinylpyridine-2,6-diyl)bis(1-allyl-5-bromo-1H-benzo[d]imidazole) ( 1 ) to the lanthanide container [Ln(hfac)₃] (Ln=La, Eu, Gd, Y, Er; H-hfac=1,1,1,5,5,5-hexafluoropentane-2,4-dione) ensures the cis-cis orientation of the two adjacent α,α′-diimine units that is required for the successful intramolecular Grubb ring-closing metathesis generating the target rigid 6-methyl-9,11-dihydro-1H,3H-2λ²,10λ²-pyrido[2,3-c:6,5-c′]bis(azepine) scaffold decorated with two terminal 5-bromo-1H-benzo[d]imidazole in ligand L7 . The bond valence analysis of the crystal structures of the associated nine-coordinate adducts [ L7 Ln(hfac)₃] (Ln=La, Eu, Gd, Er, Y) reveals a satisfying match between the rigid terdentate cavity and the size of the bound lanthanide metal, with a pronounced preference for the largest lanthanum cation. Thermodynamic studies in dichloromethane confirm the formation of [ L7 Ln(hfac)₃] adducts with unprecedented stabilities due to the removal of the energy penalty associated with trans-trans to cis-cis reorganization. The introduction of saturated methylene groups within the polyaromatic ligand backbone breaks extended aromatic delocalization and clears the visible part of the electromagnetic spectrum from emission arising from low-energy ligand-based excited states.     

The Honeysuckle and the Bindweed Revisited: Synthesis and Stereochemistry of Extended Helical Structures from Coordination Complexes

We report structural studies of a chiral tridentate ligand which forms helical cubanes with cobalt(II) and manganese(II). A quadruple helicate with (P)-chirality is obtained using a (S)-ligand with cobalt(II) but the ligand binds manganese(II) in one of two possible orientations and either (P)- or (M)-quadruple helicates may be observed for a given ligand enantiomer. The helicates may be linked into extended structures by p-nitrobenzoate capping ligands which show stacking interactions with neighbouring complexes. With cobalt(II) we find an extended helical structure with (M)-chirality linking helicates which themselves have (P)-chirality. With manganese(II) we observe a remarkable structure with extended (M)-helices coexisting with extended (P)-helices.     

Symmetry and Rigidity for Boosting Erbium-Based Molecular Light-Upconversion in Solution

Previously limited to highly symmetrical homoleptic triple-helical complexes [Er( Lk )₃]³⁺, where Lk are polyaromatic tridentate ligands, single-center molecular-based upconversion using linear optics and exploiting the excited-state absorption mechanism (ESA) greatly benefits from the design of stable and low-symmetrical [ Lk Er(hfa)₃] heteroleptic adducts (hfa⁻=hexafluoroacetylacetonate anion). Depending on (i) the extended π-electron delocalization, (ii) the flexibility and (iii) the heavy atom effect brought by the bound ligand Lk , the near-infrared (801 nm) to visible green (542 nm) upconversion quantum yield measured for [ Lk Er(hfa)₃] in solution at room temperature can be boosted by up to three orders of magnitude.     

Microdeformation in Heterogeneous Polymers,Revealed by Electron Microscopy

Recent investigations of the tensile fracture behaviour of representative glassy and semicrystalline impact-resistant polymers are reviewed, with emphasis on the microdeformation behaviour as revealed by electron microscopy of sections from bulk specimens, where the crack-tip damage zone has been embedded and/or stained under load, and on thin films deformed in situ. The insight that such techniques have provided into the toughening mechanisms is discussed.