Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7—that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal–dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

中文翻译：

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通过超材料结构作为溶剂类似物调整电荷转移动力学和非局部介电常数

电荷转移（CT）是生物学，物理和化学领域中一种基本且普遍存在的机制。在这里，我们证明多层双曲超材料（HMM）衬底可以改变CT动力学。以三亚苯基：per二酰亚胺二元超分子自组装为模型系统，我们发现存在HMM结构时寿命更长的CT状态，电荷分离和重组特征时间均增加2.4和1.7倍，即相对变化分别为140％和73％。为了根据驱动力合理化这些实验结果，我们在马库斯理论中成功引入了图像偶极子相互作用。本文证明的非局部效应与金属-电介质对的数量直接相关，可以形式化为介电常数，并作为局部溶剂极性效应的固体类似物呈现。该模型和额外的PH3T：PC60BM结果显示出这种非局部现象的普遍性，并且底物工程学可能会产生广泛的动力学调整机会。这项工作为设计用于控制光电子和化学领域中感兴趣的CT动态的人造基板的设计铺平了道路。