Self-Assembly of a Ti₄(embonate)₆ Cage toward Silver

Abstract

Herein we report a variety of supramolecular architectures that are self-assembled by the highly charged anionic Ti 4 L 6 (L = embonate) cages and noble-metal Ag + ions in the presence of the different ligands, including six Ti 4 L 6 −Ag(PPh 3 ) cages in whose structures the Ti 4 L 6 cage catches various in situ formed [Ag(PPh 3 )] + moieties by a coordination bond and one cocrystal superstructure of a Ti 4 L 6 cage with an in situ generated [Ag 2 (Ph 2 P(CH 2 ) 5 PPh 2 ) 3 ] 2+ cage via supramolecular interactions. In addition, the third-order nonlinear-optical properties of these compounds are investigated in detail.

Cage‐Ligand Strategy for the Construction of Zr4(embonate)6–Based MOFs with Third‐Order Nonlinear‐Optical Properties

“…Recently, our synthetic strategy has been to replace the commonly used one‐step method with stepwise assembly strategy. [ 28‐34 ] By using the Zr 4 L 6 (L = embonate) tetrahedron as a reactive precursor to assembly with Eu 3+ ions, a series of novel cage‐based bimetallic Zr‐Eu complexes with various dimensional architectures were synthesized by two‐step reaction. [ 32 ] Interestingly, we found that a layer structure with π − π stacking forces between L ligands shows notable optical limiting effect.…”

“…[ 32 ] Interestingly, we found that a layer structure with π − π stacking forces between L ligands shows notable optical limiting effect. In fact, the rich naphthalene rings on its surface facilitate the formation of π − π stacking interactions, [ 29,33 ] so such a tetrahedral cage (including isostructural Ti 4 L 6 cage) is regarded as an excellent building block for the construction of cage‐based MOFs with third‐order nonlinear‐optical (NLO) properties.…”

Tunable third-order nonlinear optical effect via modifying Ti4(embonate)6 cage-based ionic pairs

“…Fortunately, we firstly observed that two compounds composed of tetrahedral Ti 4 L 6 cages exhibit distinctive optical limiting effects and typical RSA responses. 49,50 In this work, we thoroughly investigate the assembly and nonlinear optical properties of anionic Ti 4 L 6 cages and various N,N-chelated transition-metal cations (Table 1). By introducing the large π-conjugated 1,10-phenanthroline type ligands and adjusting the aromatic ring electron cloud density, we effectively regulate their third-order NLO properties.…”

Chiral Co-Crystals of (S)- or (R)-1,1′-Binaphthalene-2,2′-diol and Zn2Dy2 Tetranuclear Complexes Behaving as Single-Molecule Magnets

“…As a common method of crystal engineering, eutectic methods are often used in the fields of pharmaceuticals, − energetic materials, − ferroelectrics, , nonlinear optics, − and other molecular materials. , Curiously, the vast majority of them are organic co-crystals, and there are few co-crystals involving coordination complexes because their matching potential energies and crystallization kinetics for lattice packing are difficult to satisfy. Lanthanide complexes or 3d–4f complexes are highly valued for their excellent performance in the field of SMMs. , Nevertheless, few people use eutectic methods to improve SMM properties or add other physical properties .…”