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首页> 外文期刊>Chemistry: A European journal >Light-Harvesting Phthalocyanine-Diketopyrrolopyrrole Derivatives: Synthesis, Spectroscopic, Electrochemical, and Photochemical Studies
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Light-Harvesting Phthalocyanine-Diketopyrrolopyrrole Derivatives: Synthesis, Spectroscopic, Electrochemical, and Photochemical Studies

机译：集光酞菁-二酮吡咯并吡咯衍生物：合成，光谱，电化学和光化学研究

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摘要

A new family of light-harvesting zinc phthalocyanine (ZnPc)-diketopyrrolopyrrole (DPP) hybrids have been synthesized and characterized. The absorption spectral measurements showed that the major absorptions of DPP (450-600 nm) are complementary to those of zinc phthalocyanine (300-400 and 600-700 nm). Therefore, the designed hybrids absorb over a broad range in the visible region. The geometric and electronic structures of the dyads were probed by initio B3LYP/6-311G methods. The majority of the HOMOs were found to be located on the ZnPc, while the majority of the LUMOs were on the DPP units. The DPP units serve as the antenna, which upon excitation undergo efficient singlet-singlet energy transfer to the attached ZnPc units. The formed singlet ZnPc, in turn, donates its electron to the electron-deficient DPP forming the low-lying radical ion pairs ZnPc center dot+-DPP center dot- (energy=1.44-1.56 eV as calculated from the electrochemical measurements). The excited-state events were confirmed by using a transient absorption technique in the picosecond-microsecond time range, as well as a time-resolved emission technique. The rates of energy transfer from the singlet DPP to ZnPc were found to be extremely fast > 10(10) s(-1), while the rates of electron transfer from the singlet excited state of ZnPc to DPP were found to be 3.7-6.6 x 10(9) s(-1).
机译：合成并表征了新的光采锌酞菁锌（ZnPc）-二酮吡咯并吡咯（DPP）杂种家族。吸收光谱测量表明，DPP（450-600 nm）的主要吸收与锌酞菁锌（300-400和600-700 nm）的吸收互补。因此，设计的杂种在可见光区域吸收的范围很广。通过initio B3LYP / 6-311G方法探测了二元组的几何和电子结构。发现大多数HOMO位于ZnPc上，而大多数LUMO位于DPP单元上。 DPP单元用作天线，在激发时会经历有效的单重态-单重态能量转移到连接的ZnPc单元。形成的单线态ZnPc依次将其电子捐赠给形成低位自由基离子对ZnPc中心点+ -DPP中心点-（根据电化学测量计算，能量= 1.44-1.56 eV）的缺电子DPP。通过在皮秒-微秒时间范围内使用瞬态吸收技术以及时间分辨发射技术，可以确定激发态事件。发现从单重态DPP到ZnPc的能量转移速率非常快> 10（10）s（-1），而从ZnPc的单重态激发态到DPP的电子转移速率为3.7-6.6。 x 10（9）s（-1）。

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