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Titanium‐based coordination cages could be interesting for both supramolecular and photophysical chemistry. This work reports an unprecedented host–guest system, [Ti(H2O)6]@Ti8L12, which is comprised of the first Ti‐based coordination cube and the unusual titanium aquo species. Due to the abundant intra‐cube O−H⋅⋅⋅O hydrogen bonds, the [Ti(H2O)6]@Ti8L12 complex is rather stable both in solid and solution...
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