4.7 Article

Encapsulation of Phosphorescent Pt(II) Complexes in Zn-Based Metal-Organic Frameworks toward Oxygen-Sensing Porous Materials

期刊

INORGANIC CHEMISTRY
卷 59, 期 10, 页码 7252-7264

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AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c00678

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  1. Deutsche Forschungsgemeinschaft (DFG) [396890929/GRK 2482]
  2. Deutsche Forschungsgemeinschaft [DFG: EXC1003, TRR61, STR 1186/7-1, STR 1186/6-1]
  3. WWU
  4. Alexander von Humboldt Foundation

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In this work, we synthesized two tailored phosphorescent Pt(II) complexes bearing a cyclometalating tridentate thiazole-based C<^>N*N pincer luminophore (L) and exchangeable chlorido ([PtCl(L)]) or cyanido ([PtCN(L)]) coligands. While both complexes showed photoluminescence from metal-perturbed ligand-centered triplet states ((MP)-M-3-LC), [PtCN(L)] reached the highest phosphorescence quantum yields and displayed a significant sensitivity toward quenching by O-3(2). We encapsulated them into two Zn-based metal-organic frameworks, namely, MOF-5 and ZIF-8. The incorporation of the organometallic compounds in the resulting composites [PtCl(L)]@ZIF-8, [PtCN(L)]@ZIF-8, [PtCl(L)]@moF-5, and [PtCN-(L)]@MOF-5 was verified by powder X-ray diffractometry, scanning electron microscopy, time-resolved photoluminescence spectroscopy and microscopy, as well as N-2- and Ar-gas sorption studies. The amount of encapsulated complex was determined by graphite furnace atomic absorption spectroscopy, showing a maximum loading of 3.7 wt %. If compared with their solid state forms, the solid-solution composites showed prolonged O-3(2)-sensitive excited state lifetimes for the complexes at room temperature, reaching up to 18.4 mu s under an Ar atmosphere, which is comparable with the behavior of the complex in liquid solutions or even frozen glassy matrices at 77 K.

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