Functionalization of Electrode Surfaces with Reactive Supramolecular Oligomers Enables the Control of Monolayer Properties to Restore Electrochemical Reversibility
Functionalization of Electrode Surfaces with Reactive Supramolecular Oligomers Enables the Control of Monolayer Properties to Restore Electrochemical Reversibility
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DOI：
10.1021/acs.chemmater.3c01168
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发表时间：
2023-08
影响因子：
8.6
通讯作者：
Ifigeneia Tsironi;Jarek A. Maleszka;Robert S. Wilson‐Kovacs;Victor A. Paulino;O. Acevedo;Arindam Mukhopadhyay;Jean‐Hubert Olivier
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文献类型：
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作者：
Ifigeneia Tsironi;Jarek A. Maleszka;Robert S. Wilson‐Kovacs;Victor A. Paulino;O. Acevedo;Arindam Mukhopadhyay;Jean‐Hubert Olivier
利用氧化还原活性探针对导电硅（Si）衬底进行功能化，可获得电子功能由单层分子构象参数化的杂化半导体界面。然而，利用易于聚集的平面π共轭衍生物构建电子均匀的半导体界面仍然具有挑战性，因为固体中的结构非均质性明确地产生了不明确的电子域。众所周知，这一限制阻碍了来自乙烯染料的n型半导体Si界面的发展，这些界面在太阳能捕获和转换中具有诱人的应用。本文通过使用反应性萘二亚胺（NDI）单元衍生的超分子低聚物作为结构模板来控制Si界面上半导体单层的电化学响应，克服了这一挑战。具体来说，与来自分子衍生前体的半导体界面相比，用NDI非共价组件功能化的导电Si表面表现出可逆的电化学信号和稳定在100 mV以上的还原电位。利用密度泛函理论和分子动力学模拟，实验记录的电位性质被分配到离散的NDI构象，这些构象由溶液中前驱体的聚集状态参数化。这些发现描述了一种新的策略来控制半导体界面的电子结构均匀性，这些半导体界面是由众所周知的形成不明确的电子域的染料构成的。
The functionalization of conducting silicon (Si) substrates with redox-active probes delivers hybrid semiconducting interfaces whose electronic functions are parameterized by the molecular conformations of monolayers. However, it remains challenging to build electronically homogeneous semiconducting interfaces using flat, π-conjugated derivatives that are prone to aggregation, as structural heterogeneity in the solid state unequivocally engenders ill-defined electronic domains. This limitation has notoriously hampered the development of n-type semiconducting Si interfaces derived from rylene dyes, which possess enticing applications in solar energy capture and conversion. Herein, this challenge is overcome by using supramolecular oligomers derived from reactive naphthalene diimide (NDI) units as structural templates to control the electrochemical response of semiconducting monolayers at Si interfaces. Specifically, conducting Si surfaces functionalized with NDI noncovalent assemblies exhibit reversible electrochemical signals and reduction potentials stabilized by more than 100 mV compared to semiconducting interfaces derived from molecularly derived precursors. Leveraging density functional theory and molecular dynamics simulations, the potentiometric properties recorded experimentally are assigned to discrete NDI conformations, which are parameterized by the aggregation state of the precursors in solution. These findings delineate a novel strategy to control the electronic structure homogeneity of semiconducting interfaces constructed from dyes infamously known to form ill-defined electronic domains.