A Bowl‐Shaped Circular Trinuclear Helicate Generated from a TiO₄N₂ Motif by a Multicomponent Self‐Assembly Approach

Abstract

The synthesis of a bowl-shaped trinuclear circular titanium-based helicate is reported. The strategy allowing access to this neutral architecture is based on a multicomponent self-assembly approach in which the ligands involved in the process are a bis-biphenol strand and 2,2'- bipyrimidine. By reacting the bis-biphenol ligand and 2,2'-bipyrimidine with an equimolar amount [Ti(OiPr)4 ], a bowl-shaped architecture is obtained through the formation of 18 new coordination bonds. This aggregate built from three octahedral TiO4 N2 nodes displays an unusually high stability in solution compared to related species. In addition, by modifying the stoichiometry of the initial components, two assemblies incorporating two titanium centers bridged by a 2,2'-bipyrimidine ligand are obtained. The crystal structures of these species are reported.

Monomeric Ti(iv)-based complexes incorporating luminescent nitrogen ligands: synthesis, structural characterization, emission spectroscopy and cytotoxic activities

“…The Λ-[Ti(1) 2 (2a)] enantiomer is observed in the analyzed crystal. The Flack parameter of 0.006 (15) determined for the Λ-[Ti(1) 2 (2a)] structure resolution confirms the absolute configuration attribution. Concerning the molecular structures description, it is worth noticing that the aromatic units substituting the bipyrimidine ligands in [Ti(1) 2 (2b)] and [Ti(1) 2 (2c)] are coplanar to the neighbouring pyrimidine ring.…”

“…13 In metallo-supramolecular chemistry, titanium(IV) centers are intensively employed to create self-assembled architectures from oxygen ligands 14 or from multiple components. 15 Applications of titanium(IV) complexes in bioinorganic chemistry are also deeply investigated, as long as titanium(IV) is recognized for its low toxicity for living matter. Therefore, titanium is found in many biomaterials and numerous applications of Ti(IV) in a medical or biological context have been described.…”

Crystalline bis(η5-cyclopentadienyl)bis(benzoato/carboxylato)titanium(IV) precursor-directed route to functional titanium dioxide nanomaterials

“…Titanium(IV) complexes form a major class of organometallic and coordination compounds which display effective and tuneable reactivities [1][2][3]. These compounds are also marked as effective catalysts [4][5][6][7][8], have featured in metallo-supramolecular chemistry [9,10] and have applications in medicinal and bioinorganic chemistry [11,12]. Among the latter, Cp2TiCl2 was investigated as an anti-cancer drug, based on the presence of the dichloride entity under the assumption its mode of biological action would be closely aligned with that of cisplatin, [cis-PtCl2(NH3)2].…”

Linear and circular helicates: A brief review

“…Further, the neutral zinc(II) cyclic helicate can also be completely disassembled by H 2 PO 4 ions ( Figure 30). Mobian et al, reported the synthesis of a titanium-based bowl-shaped trinuclear circular helicate, 35 36. A multicomponent self-assembly approach involving bis-biphenol strand (H 4 L36a) and 2, 2 -bipyrimidine (L36b) as ligands and [Ti(OiPr) 4 ], was used to synthesize this neutral architecture with C 3 symmetry.…”