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Charge-separation in panchromatic, vertically positioned bis(donor styryl)BODIPY–aluminum(iii) porphyrin–fullerene supramolecular triads†
Nanoscale ( IF 6.7 ) Pub Date : 2018-10-12 00:00:00 , DOI: 10.1039/c8nr06649c
Niloofar Zarrabi 1, 2, 3, 4 , Christopher O. Obondi 4, 5, 6, 7 , Gary N. Lim 4, 5, 6, 7 , Sairaman Seetharaman 4, 5, 6, 7 , Benjamin G. Boe 1, 2, 3, 4 , Francis D'Souza 4, 5, 6, 7 , Prashanth K. Poddutoori 1, 2, 3, 4
Affiliation  

Three, broad band capturing, vertically aligned supramolecular triads, R2-BDP-AlPorF3←Im-C60 [R = H, styryl (C2H2-Ph), C2H2-TPA (TPA = triphenylamine); ← = coordinate bond], have been constructed using BODIPY derivative (BDP, BDP-Ph2 or BDP-TPA2), 5,10,15,20-tetrakis(3,4,5-trifluorophenyl)aluminum(III) porphyrin (AlPorF3) and fullerene (C60) entities. The C60 and BDP units are bound to the Al center on the opposite faces of the porphyrin: the BDP derivative through a covalent axial bond using a benzoate spacer and the C60 through a coordination bond via an appended imidazole. Owing to the bis-styryl functionality on BDP, the constructed dyads and triads exhibited panchromatic light capture. Due to the diverse absorption and redox properties of the selected entities, it was possible to demonstrate excitation wavelength dependent photochemical events. In the case of the BDP-AlPorF3 dyad, selective excitation of BDP resulted in singlet–singlet energy transfer to AlPorF3 (kEnT = 1.0 × 1010 s−1). On the other hand, excitation of the AlPorF3 entity in the BDP-AlPorF3←Im-C60 triad revealed charge separation leading to the BDP-(AlPorF3+-(C60 charge separated state (kCS = 2.43 × 109 s−1). In the case of the Ph2-BDP-AlPorF3 dyad, energy transfer from 1AlPorF3* to 1(Ph2-BDP)* was witnessed (kEnT = 1.0 × 1010 s−1); however, upon assembling the supramolecular triad, (Ph2-BDP)-AlPorF3←Im-C60, electron transfer from 1AlPorF3* to C60 (kCS = 3.35 × 109 s−1), followed by hole shift (kHS = 1.00 × 109 s−1) to Ph2-BDP, was witnessed. Finally, in the case of the TPA2-BDP-AlPorF3←Im-C60 triad, only electron transfer leading to the (TPA2-BDP)˙+-AlPorF3←Im-(C60 charge separated state, and no energy transfer, was observed. The facile oxidation of Ph2-BDP and TPA2-BDP compared to AlPorF3 in the latter two triads facilitated charge separation through either an electron migration or hole transfer mechanism depending on the initial excitation. The charge-separated states in these triads persisted for about 20 ns.

中文翻译:

全色垂直放置的双(施主苯乙烯基)BODIPY-铝(iii)卟啉-富勒烯超分子三元组的电荷分离

三,宽带捕获,垂直排列的超分子三元组,R 2 -BDP-AlPorF 3 ←Im-C 60 [R = H,苯乙烯基(C 2 H 2 -Ph),C 2 H 2 -TPA(TPA =三苯胺);←=配位键],已使用BODIPY衍生物(BDP,BDP-Ph 2或BDP-TPA 2),5,10,15,20-四(3,4,5-三氟苯基)铝(III)卟啉( AlPorF 3)和富勒烯(C 60)实体。C 60BDP单元和BDP单元在卟啉相对表面的Al中心键合:BDP衍生物通过使用苯甲酸酯间隔基的共价轴向键结合,而C 60通过配位键通过附加的咪唑结合。由于BDP上的双苯乙烯基功能,所构建的二元组和三元组显示出全色光捕获。由于所选实体的吸收和氧化还原特性各不相同,因此有可能证明激发波长依赖的光化学事件。对于BDP-AlPorF 3二重体,BDP的选择性激发导致单重态-单重态能量转移到AlPorF 3k EnT = 1.0×10 10 s -1)。在另一方面,所述AlPorF的激励3在BDP-AlPorF实体3 ←林-C 60三联揭示电荷分离导致BDP-(AlPorF 3)˙ + - (C 60)˙ -电荷分离状态(ķ CS = 2.43×10 9 s -1)。在Ph 2 -BDP-AlPorF 3 dyad的情况下,见证了从1 AlPorF 3 *到1(Ph 2 -BDP)*的能量转移(k EnT = 1.0×10 10 s -1); 然而,在组装超分子三重态(Ph 2 -BDP)-AlPorF 3 ←Im-C 60时,电子从1 AlPorF 3 *转移到C 60k CS = 3.35×10 9 s -1),随后发生空穴移位观察到(k HS = 1.00×10 9 s -1)至Ph 2 -BDP。最后,在TPA 2 -BDP-AlPorF 3 ←Im-C 60三元组的情况下,仅电子转移导致(TPA 2 -BDP)˙ + -AlPorF 3←IM-(C 60)˙ -电荷分离状态,并且没有能量转移,观察到。在后两个三单元组中,与AlPorF 3相比,Ph 2 -BDP和TPA 2 -BDP的容易氧化,取决于初始激发,通过电子迁移或空穴传输机制促进了电荷分离。这些三单元组中的电荷分离状态持续约20 ns。
更新日期:2018-10-12
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