Polypyridine-based ruthenium complexes are among the most interesting photoactive molecular systems, in virtue of a number of outstanding (photo)physicochemical properties. To exploit such properties in solid-state applications, such as molecular electronics, optoelectronics, and photovoltaics, tailored experimental strategies are needed for the anchoring of such complexes on surfaces. At the same time, these strategies need to be investigated and validated through precise monitoring of the surface composition. In this contribution, the authors report on the application of time-of-flight secondary ion mass spectrometry (ToF-SIMS) for studying the anchoring onto transparent (semi)conducting fluorine tin-doped oxide of the polypyridinic photoactive RuDT2. This molecule is characterized by an Ru(tpy)2 core and two free terpyridinic units. The authors’ approach involves the use of a surface priming strategy based on the chemistry of zirconium phosphates and phosphonates (ZP-priming) to provide a platform for direct anchoring of RuDT2 molecules at the oxide surface. Onto patterned ZP-fluorine-doped tin oxide (FTO), the authors report selective anchoring of RuDT2 only onto ZP domains, while no binding occurs onto bare FTO areas. The latter were shown to remain available for further functionalization using functional molecules containing phosphonic moieties, and in the authors’ case, a phosphonic derivative of rhodamine B (RhB-P) was used. ToF-SIMS imaging was intensively used to monitor each reaction step and confirm the successful laterally resolved and selective adsorption of RuDT2 and RhB-P onto ZP and bare FTO domains, respectively.

中文翻译：

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磷酸锆功能化氧化物表面选择性锚定 Ru(tpy)2 配合物的 ToF-SIMS 研究

聚吡啶基钌配合物是最令人感兴趣的光活性分子系统之一，因为它具有许多出色的（光）物理化学特性。为了在固态应用（如分子电子学、光电子学和光伏学）中利用这些特性，需要量身定制的实验策略来将此类复合物锚定在表面上。同时，需要通过对表面成分的精确监测来研究和验证这些策略。在这篇文章中，作者报告了飞行时间二次离子质谱 (ToF-SIMS) 在研究多吡啶光活性 RuDT2 透明（半）导电氟锡掺杂氧化物上的锚定的应用。该分子的特征在于一个 Ru(tpy)2 核心和两个游离的三联吡啶单元。作者的方法涉及使用基于磷酸锆和膦酸锆（ZP-priming）化学的表面引发策略，为 RuDT2 分子直接锚定在氧化物表面提供平台。作者报告说，在图案化的 ZP 掺氟氧化锡 (FTO) 上，RuDT2 仅选择性锚定在 ZP 域上，而在裸 FTO 区域上没有发生结合。后者被证明仍可用于使用含有膦酸部分的功能分子进行进一步功能化，在作者的情况下，使用了罗丹明 B (RhB-P) 的膦酸衍生物。ToF-SIMS 成像被广泛用于监测每个反应步骤，并确认 RuDT2 和 RhB-P 分别成功地横向解析和选择性吸附到 ZP 和裸 FTO 域上。