Titanium oxo clusters
(TOCs) are the well-defined molecular modes
for TiO2 materials and provide the opportunity to clarify
the relationships between the structures and properties of TiO2. Here, we report a large titanium oxo cluster {Ti
14
} featuring a well-defined
structural unit of rutile by a solvent-thermal reaction of Ti(O
i
Pr)4, acetic acid, and 1,10-phenanthroline.
Crystal structural analysis showed that the 14 Ti4+ ions
are connected by 19 bridging oxo ligands, forming a double-decked
hexagonal prism structure passivated with acetate and chelate 1,10-phenanthroline
ligands. The {Ti
14
} cluster displays a high photocatalytic H2 production
activity because of the conjugated chromophore ligands.
Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi‐component building block [Ln3Ti(HSA)6(SA)4(H2O)]− ({Ln3Ti‐SA}, H2SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln3Tix‐MSA} (H2MSA=5‐methoxysalicylic acid, x=1, 2, 3) by constructing [Ti(MSA)3]2− units. The obtained {Ln3Tix‐MSA} can further assemble into a chiral Ln22Ti14 ring with the formulae [Eu22Ti14(MSA)48(HMSA)22(CH3COO)4(H2O)10(iPrOH)] and [Gd22Ti14(MSA)46(HMSA)26(CH3COO)4(H2O)8]. Parallel experiments without Ti4+ result in linear Ln chains. Detailed analysis shows that the [Ti(MSA)4]4− unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA)3]2− further triggers interesting chiral‐sorting behavior. Finally, the electronic adsorption and magneto‐optic responses of these molecular rings are investigated.
A series of high-nuclearity 3d–4f clusters Ln45M7 were obtained based on acetate and propionate as mixed protecting ligands and ClO4− and CO32− as mixed anion templates.
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