Host–Guest and Photophysical Behavior of Ti8L12 Cube with Encapsulated [Ti(H2O)6] Species. Issue 54 (3rd September 2018)

• Record Type: Journal Article
• Authors: Zhu, Bang‐Chang; Fang, Wei‐Hui; Wang, Junhui; Du, Yonghua; Zhou, Tianhua; Wu, Kaifeng; Zhang, Lei; Zhang, Jian
• Is Part Of: Chemistry. Volume 24:Issue 54(2018)
• Page Start: 14358
• Page End: 14362
• Publication Date: 2018-09-03
• Subjects: cage compounds -- coordination assembly -- host–guest systems -- photophysics -- titanium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201802930
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Titanium‐based coordination cages could be interesting for both supramolecular and photophysical chemistry. This work reports an unprecedented host–guest system, [Ti(H2 O)6 ]@Ti8 L12, 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(H2 O)6 ]@Ti8 L12 complex is rather stable both in solid and solution states, confirmed by X‐ray diffraction and ESI‐MS analysis. The encapsulated [Ti(H2 O)6 ] species shows influence on the light absorption, photoluminescent, and photocurrent properties. Moreover, ultrafast transient absorption spectroscopy has been applied to study the photodynamics of both free and [Ti(H2 O)6 ] guest encapsulated Ti8 L12 cube, confirming that the host–guest system produces a slightly longer‐lived excited state. Therefore, this work presents the first [Ti8 L12 ] cube with unusual [Ti(H2 O)6 ] guest and also provides an interesting supramolecular model for the host–guest photophysical study. Abstract : The first Ti8 L12 cube was assembled that could further encapsulate an unprecedented [Ti(H2 O)6 ] species. Electrospray ionization (ESI) analysis confirmed high solution stability of the supramolecular system. Host–guest hydrogen‐bonding interactions resulted in differences in photophysical behavior such as redshifted absorption and luminescent bands, larger photocurrents, and longer excited‐state lifetime.