Charge Stabilization in High-Potential Zinc Porphyrin-Fullerene via Axial Ligation of Tetrathiafulvalene
Charge Stabilization in High-Potential Zinc Porphyrin-Fullerene via Axial Ligation of Tetrathiafulvalene
复制标题
DOI：
10.1021/acs.jpcc.8b00028
复制
发表时间：
2018-01
影响因子：
3.7
通讯作者：
C. Obondi;Gary N. Lim;Y. Jang;Prajay Patel;A. Wilson;P. Poddutoori;F. D’Souza
中科院分区：
文献类型：
--
作者：
C. Obondi;Gary N. Lim;Y. Jang;Prajay Patel;A. Wilson;P. Poddutoori;F. D’Souza
通过吡啶功能化的四硫富瓦烯（TTF）与金属配体的轴向配位，通过双电子转移/空穴迁移机制，延长了高电位锌卟啉-富勒烯二元体系（F15 P）Zn-C60在光诱导电子转移过程中产生的电荷分离态的寿命.锌卟啉的meso-芳基位置带有三个五氟苯基取代基，使锌卟啉环更难氧化，与meso-苯基取代基的锌卟啉相比，其氧化电位降低了0.43 V。两种TTF衍生物，第一种具有直接连接到TTF的吡啶（Py-TTF），第二种具有在吡啶和TTF之间的苯基间隔基（Py-phTTF），用于改变初级光敏剂/电子供体锌卟啉和次级电子供体TTF之间的距离。Py-TTF和Py-phTTF都通过吡啶实体与Zn中心配位，具有1：1的分子化学计量比和中等的结合常数。超分子三元组
Extending the lifetime of the charge-separated states generated during photoinduced electron transfer in a covalently linked high-potential zinc porphyrin-fullerene dyad, (F15P)Zn–C60, was accomplished by metal–ligand axial coordination of pyridine-functionalized tetrathiafulvalene (TTF) via a dual-electron-transfer/hole migration mechanism. The meso-aryl positions of the zinc porphyrin carried three penta-fluorophenyl substituents that made the zinc porphyrin ring harder to oxidize by 0.43 V compared with zinc porphyrin with meso-phenyl substituents. Two TTF derivatives, a first with a pyridine directly linked to TTF (Py-TTF) and a second with a phenyl spacer between the pyridine and TTF (Py-phTTF), were employed to vary the distance between the primary photosensitizer/electron donor, zinc porphyrin, and the secondary electron donor, TTF. Both Py-TTF and Py-phTTF coordinated via the pyridine entity to the Zn center with 1:1 molecular stoichiometry and moderate binding constants. The supramolecular triads...