N,N′-Dimethylene-2,2′-biimidazole—A Mimic of Carboxylate for the Formation of Complexes with Copper(I) And the Anion Directed Formation of a Solvent Pocket

Abstract

The reaction of N,N′-dimethylene-2,2′-biimidazole (L) with various copper salts gives eight complexes that were characterized structurally in the solid state. This showed that the ligand can effectively bridge two copper atoms in close proximity similarly to the well-known bridging carboxylate motif. In reaction with copper(II), this gives a dimer (acetate, 1) or quadruple helicate (perchlorate, 2). Extention to copper(I) with a coordinating counterion gives a one-dimensional polymer (iodide, 3), while reaction with noncoordinating counterion gives M2L3 triple helicate motifs. These helicates were found to form chiral solvate-containing pockets surrounding benzene when combined with a three-fold symmetric anion (BF4 –, ClO4 – and NO3 –, 4, 5, and 6, respectively) or an achiral complex with only acetonitrile (ClO4 –, 7). While the pocket could accommodate fluorobenzene (BF4 –, 8), more highly substituted benzenes do not allow its formation.

Molecular Scylla and Charybdis: Maneuvering between pH Sensitivity and Excited-State Localization in Ruthenium Bi(benz)imidazole Complexes

“…Upon the bridge is changed from ethylene to propylene, the two (benz)­imidazole spheres become planarized, as reflected by a smaller dihedral angle δ bim for prbim and prbbim compared to etbim and etbbim . , Because this trend was not observed by others, , adaption of these dihedral angles to the direct molecular environment seems feasible.…”

“…Comparison of the Solid-State Structures of Ruprbim and prbim and Literature-Known Ruthenium Complex Derivatives. Contrary to the above-discussed rigid ethylene protection groups, 40,41 the propylene bridge may allow a certain degree of distortion of the bim scaffold. In order to verify this hypothesis, we analyzed an obtained single-crystal Xray diffraction structure of Ruprbim (Figure 4).…”

Ligand Coordination Site-Directed Assembly of Copper(I) Iodide Complexes of ((Pyridyl)-1-pyrazolyl)pyridine

“…In the past decades, copper­(I) complexes with nitrogen, phosphorus, and sulfur organic ligands have been extensively investigated because of their interesting structures and photochemical, photophysical properties. − Copper­(I) iodide complexes, in particular, demonstrate rich photophysical behavior which could be manipulated by a wide variety of cluster chromophores [Cu n I n ] − and the supporting organic ligands. With regard to N-heterocyclic organic ligands, poly­(pyridyl), − ,− ,,, poly­(triazolyl), − poly­(imidazolyl), − pyrazine, − poly­(pyrazolyl), − and poly­(benzimidazolyl) , have been extensively employed in the assembly of the [Cu n I...…”