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“Hetero‐Multifunctionalization” of Gallium Corroles: Facile Synthesis, Phosphorescence, Redox Tuning, and Photooxidative Catalytic Improvement
Author(s) -
Zhan Xuan,
Zini Yael,
Fridman Natalia,
Chen QiuCheng,
Churchill David G.,
Gross Zeev
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201900667
Subject(s) - phosphorescence , chemistry , gallium , catalysis , redox , photochemistry , halogenation , medicinal chemistry , polymer chemistry , inorganic chemistry , organic chemistry , physics , quantum mechanics , fluorescence
Bromination of tris‐ and tetrakis‐trifluoromethylated gallium corroles ( 3CF 3 −Ga and 4CF 3 −Ga ) afforded tetrabrominated species 3CF 3 −4Br−Ga and 4CF 3 −4Br−Ga (yields: 20 % and 25 %) characterized by NMR, UV‐vis spectroscopy, and mass spectrometry. Red‐shifted absorption and emission bands were found; 3CF 3 −4Br−Ga and 4CF 3 −4Br−Ga displayed 5–12 nm shifts in their Soret bands and 8–17 nm shifts for their Q bands, compared to the respective nonbrominated species ( 3CF 3 −Ga and 4CF 3 −Ga ). The respective Φ F values were found to be 0.013 and 0.016; phosphorescence (lifetime=0.23 μs) was observed for 3CF 3 −4Br−Ga (anaerobic, RT). The effect of tetrabromination on redox potentials (0.89 and 0.99 V) gave a 85 mV shift per Br atom in the reduction potential. 4CF 3 −4Br−Ga allows for efficient catalytic photooxidative Br − to Br 2 conversion compared to the β‐octa‐Br system ( Br 8 −Ga ) structurally characterized here. This “hetero‐multifunctionalization” approach, that is, is substitution with different sets of β‐substituents, can help optimize porphyrinoid properties.