当前位置: X-MOL 学术ChemPlusChem › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
“Hetero‐Multifunctionalization” of Gallium Corroles: Facile Synthesis, Phosphorescence, Redox Tuning, and Photooxidative Catalytic Improvement
ChemPlusChem ( IF 3.4 ) Pub Date : 2019-12-12 , DOI: 10.1002/cplu.201900667
Xuan Zhan 1 , Yael Zini 1 , Natalia Fridman 1 , Qiu‐Cheng Chen 1 , David G. Churchill 1, 2, 3, 4 , Zeev Gross 1
Affiliation  

Bromination of tris‐ and tetrakis‐trifluoromethylated gallium corroles (3CF3−Ga and 4CF3−Ga) afforded tetrabrominated species 3CF3−4Br−Ga and 4CF3−4Br−Ga (yields: 20 % and 25 %) characterized by NMR, UV‐vis spectroscopy, and mass spectrometry. Red‐shifted absorption and emission bands were found; 3CF3−4Br−Ga and 4CF3−4Br−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 (3CF3−Ga and 4CF3−Ga). The respective ΦF values were found to be 0.013 and 0.016; phosphorescence (lifetime=0.23 μs) was observed for 3CF3−4Br−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. 4CF3−4Br−Ga allows for efficient catalytic photooxidative Br to Br2 conversion compared to the β‐octa‐Br system (Br8−Ga) structurally characterized here. This “hetero‐multifunctionalization” approach, that is, is substitution with different sets of β‐substituents, can help optimize porphyrinoid properties.

中文翻译:

镓杂化物的“杂多官能化”:简便的合成,发磷光,氧化还原调节和光氧化催化改进

三氟和四氟甲基化的镓腐蚀物(3CF 3 -Ga4CF 3 -Ga)的溴化得到四溴化的物质3CF 3 -4Br-Ga4CF 3 -4Br-Ga(收率:20%和25%),通过NMR表征,紫外可见光谱和质谱 发现了红移的吸收带和发射带;与各自的非溴化物种相比,3CF 3 -4Br-Ga4CF 3 -4Br-Ga在它们的Soret带中显示了5–12 nm的位移,在Q带中显示了8–17 nm的位移(3CF 3 -Ga4CF 3 -Ga)。相应Φ ˚F发现值是0.013和0.016; 对于3CF 3 -4Br-Ga(厌氧,RT)观察到磷光(寿命= 0.23μs)。四溴化对氧化还原电位(0.89和0.99 V)的影响使还原电位中每个Br原子偏移85 mV。4CF 3 -4Br -镓允许有效催化光氧化溴-为BR 2的转换相比,β -辛溴系统(8 -Ga)的结构特点。这种“杂多功能化”方法,即用不同的β-取代基取代,可以帮助优化卟啉类化合物的性质。
更新日期:2019-12-13
down
wechat
bug