Exciton Transfer Between Extended Electronic States in Conjugated Inter-Polyelectrolyte Complexes
Exciton Transfer Between Extended Electronic States in Conjugated Inter-Polyelectrolyte Complexes
复制标题
共轭间聚电解质复合物中扩展电子态之间的激子转移
DOI：
10.1021/acsami.3c14657
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发表时间：
2024
影响因子：
9.5
通讯作者：
Ayzner, Alexander L.
中科院分区：
文献类型：
--
作者：
Richards, Rachael;Song, Yuqi;O’Connor, Luke;Wang, Xiao;Dailing, Eric A.;Bragg, Arthur E.;Ayzner, Alexander L.
人工采光是一种将阳光转化为化学势能的过程，被认为是应对紧迫的全球能源挑战的整体解决方案中很有前途的一部分。共轭聚电解质络合物(CPECs)由于其扩展的电子态、可调的组装热力学和对局部环境的敏感性而特别吸引人。重要的是，共轭聚电解质的离子组装络合物可以作为有效的电子能量转移(EET)的供体-受体对。然而，为了在材料应用中使用，我们必须了解改变CPE主干的化学结构如何改变EET速率，而不是考虑光谱重叠。在这份报告中，我们研究了EET效率和速率与CPE主链的电子结构和激子波函数的关系。为此，我们合成了一系列交替共聚物，通过引入具有吸电子和富电子特性的共聚单体来系统地改变电子状态，同时保持线性离子电荷密度几乎不变。根据基于线偶极子近似的分析模型和量子化学计算，我们发现激子耦合可能受到激子离域半径的显著影响。我们的结果表明，在选择CPE组件时应谨慎选择最佳的CPEC EET。这些结果对将CPECs用作水基捕光材料的关键成分具有重要意义，无论是作为独立的组件还是作为纳米颗粒和薄膜的吸附。
Artificial light harvesting, a process that involves converting sunlight into chemical potential energy, is considered to be a promising part of the overall solution to address urgent global energy challenges. Conjugated polyelectrolyte complexes (CPECs) are particularly attractive for this purpose due to their extended electronic states, tunable assembly thermodynamics, and sensitivity to their local environment. Importantly, ionically assembled complexes of conjugated polyelectrolytes can act as efficient donor–acceptor pairs for electronic energy transfer (EET). However, to be of use in material applications, we must understand how modifying the chemical structure of the CPE backbone alters the EET rate beyond spectral overlap considerations. In this report we investigate the dependence of the EET efficiency and rate on the electronic structure and excitonic wave function of the CPE backbone. To do so, we synthesized a series of alternating copolymers where the electronic states are systematically altered by introducing comonomers with electron withdrawing and electron-rich character while keeping the linear ionic charge density nearly fixed. We find evidence that the excitonic coupling may be significantly affected by the exciton delocalization radius, in accordance with analytical models based on the line-dipole approximation and quantum chemistry calculations. Our results imply that care should be taken when selecting CPE components for optimal CPEC EET. These results have implications for using CPECs as key components in water-based light-harvesting materials, either as standalone assemblies or as adsorbates on nanoparticles and thin films.
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DOI：
10.1021/la1011764
发表时间：
2010
期刊：
Langmuir : the ACS journal of surfaces and colloids
影响因子：
--
作者：
M. Monteserín;H. Burrows;R. Mallavia;R. D. Di Paolo;A. Maçanita;M. J. Tapia
通讯作者：
M. J. Tapia
影响因子：
8.6
作者：
Johnston, Anna R.;Perry, Sarah L.;Ayzner, Alexander L.
通讯作者：
Ayzner, Alexander L.
影响因子：
41.2
作者：
Vogelsang, Jan;Adachi, Takuji;Barbara, Paul F.
通讯作者：
Barbara, Paul F.
影响因子：
2.9
作者：
Barford, William
通讯作者：
Barford, William
影响因子：
2.9
作者：
Humphrey, W;Dalke, A;Schulten, K
通讯作者：
Schulten, K