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Accessing Photoredox Transformations with an Iron(III) Photosensitizer and Green Light
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-09-16 , DOI: 10.1021/jacs.1c06081 Akin Aydogan 1 , Rachel E Bangle 2 , Alejandro Cadranel 3, 4, 5 , Michael D Turlington 2 , Daniel T Conroy 2 , Emilie Cauët 6 , Michael L Singleton 1 , Gerald J Meyer 2 , Renato N Sampaio 7 , Benjamin Elias 1 , Ludovic Troian-Gautier 1, 2, 8
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-09-16 , DOI: 10.1021/jacs.1c06081 Akin Aydogan 1 , Rachel E Bangle 2 , Alejandro Cadranel 3, 4, 5 , Michael D Turlington 2 , Daniel T Conroy 2 , Emilie Cauët 6 , Michael L Singleton 1 , Gerald J Meyer 2 , Renato N Sampaio 7 , Benjamin Elias 1 , Ludovic Troian-Gautier 1, 2, 8
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Efficient excited-state electron transfer between an iron(III) photosensitizer and organic electron donors was realized with green light irradiation. This advance was enabled by the use of the previously reported iron photosensitizer, [Fe(phtmeimb)2]+ (phtmeimb = {phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate}, that exhibited long-lived and luminescent ligand-to-metal charge-transfer (LMCT) excited states. A benchmark dehalogenation reaction was investigated with yields that exceed 90% and an enhanced stability relative to the prototypical photosensitizer [Ru(bpy)3]2+. The initial catalytic step is electron transfer from an amine to the photoexcited iron sensitizer, which is shown to occur with a large cage-escape yield. For LMCT excited states, this reductive electron transfer is vectorial and may be a general advantage of Fe(III) photosensitizers. In-depth time-resolved spectroscopic methods, including transient absorption characterization from the ultraviolet to the infrared regions, provided a quantitative description of the catalytic mechanism with associated rate constants and yields.
中文翻译：
使用铁 (III) 光敏剂和绿光进行光氧化还原转化
通过绿光照射实现了铁 (III) 光敏剂和有机电子供体之间的有效激发态电子转移。这一进步是通过使用先前报道的铁光敏剂 [Fe(phtmeimb) 2 ] + (phtmeimb = {phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate} 实现的，它表现出长寿命和发光配体到金属电荷转移 (LMCT) 激发态。研究了基准脱卤反应，产率超过 90% 并且相对于原型光敏剂 [Ru(bpy) 3 ] 2+具有增强的稳定性. 最初的催化步骤是将电子从胺转移到光激发的铁敏化剂，这表明以大的笼逃逸率发生。对于 LMCT 激发态，这种还原电子转移是矢量的，可能是 Fe(III) 光敏剂的普遍优势。深入的时间分辨光谱方法，包括从紫外到红外区域的瞬态吸收表征，提供了催化机制的定量描述以及相关的速率常数和产率。
更新日期：2021-09-29
中文翻译：
使用铁 (III) 光敏剂和绿光进行光氧化还原转化
通过绿光照射实现了铁 (III) 光敏剂和有机电子供体之间的有效激发态电子转移。这一进步是通过使用先前报道的铁光敏剂 [Fe(phtmeimb) 2 ] + (phtmeimb = {phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate} 实现的，它表现出长寿命和发光配体到金属电荷转移 (LMCT) 激发态。研究了基准脱卤反应，产率超过 90% 并且相对于原型光敏剂 [Ru(bpy) 3 ] 2+具有增强的稳定性. 最初的催化步骤是将电子从胺转移到光激发的铁敏化剂，这表明以大的笼逃逸率发生。对于 LMCT 激发态，这种还原电子转移是矢量的，可能是 Fe(III) 光敏剂的普遍优势。深入的时间分辨光谱方法，包括从紫外到红外区域的瞬态吸收表征，提供了催化机制的定量描述以及相关的速率常数和产率。
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