Photophysical and photoelectric properties of phthalocyanine-based MOF thin films

为SPP第二个资助期提出的项目的总体目标是在导电和/或透明基板上制造基于发色团的结晶和定向MOF薄膜（SURMOFs）。除了卟啉（PP）之外，我们还将研究酞菁（PC）和四氮杂卟啉（PY），这两种化合物都能吸收较长的波长，因此与在上一个资助期内成功研究的PP很好地互补。单片SURMOF涂层将使用物理和电化学方法进行表征。在选定的情况下，这些薄膜将被集成到用于特定应用的设备中，例如用于光化学。这项工作将补充在第一个资助期内积极开展的基于PP的SURMOFs的成功项目，并将利用PC和PY的更高稳定性用于器件制造，特别是在光化学和光电化学领域。我们在上一个资助期间从PP基SURMOF物理性质的理论描述中获得的经验将用于筛选大量的PC和PY。该步骤是强制性的，因为PC和PY的合成与PP的情况一样更具挑战性。只有最有前途的PC和PY候选人，然后将被合成和用于制造SURMOFs。此外，逐层SURMOF生长过程允许携带不同吸收范围的染料的SURMOF的分级生长。在增加的波长范围内具有吸收的PP、PC和PY的连续堆叠将允许设计覆盖从紫外到红外的整个太阳光谱的光伏器件。

The overarching goal of the project proposed for the second funding period of the SPP is the fabrication of chromophore-based, crystalline and oriented MOF thin films (SURMOFs) on conducting and/or transparent substrates. Besides porphyrins (PPs), we will study phthalocyanines (PCs) and porphyrazines (PYs), both absorbing at longer wavelengths and hence nicely complementary to the PPs, which were successfully studied during the previous funding period. The monolithic SURMOF coatings will be characterized using photophysical and electrochemical methods. In selected cases, these films will be integrated in devices for specific applications, e.g. for photovoltaics. This work will complement the successful project on PP-based SURMOFs active during the first funding period and will exploit the higher stability of PCs and PYs for device fabrication, in particular in the area of photovoltaics and photo-electrochemistry. Our experience gained with the theoretical description of PP-based SURMOF photophysical properties during the previous funding period will be used to screen a large number of PCs and PYs in silico. This step is mandatory, since the synthesis of PCs and PYs is much more challenging as in case of the PPs. Only the most promising PC and PY candidates will then be synthesized and used to fabricate SURMOFs. Moreover, the layer-by-layer SURMOF growth process allows the hierarchical growth of SURMOFs carrying dyes of different absorption range. Consecutive stacking of PPs, PCs and PYs with absorption in increasing wavelength ranges will allow the design of photovoltaic devices with covering the entire solar spectrum, ranging from ultraviolet to infrared.