Establishing design principles for emissive organic SWIR chromophores from energy gap laws.
Establishing design principles for emissive organic SWIR chromophores from energy gap laws.
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DOI：
10.1016/j.chempr.2021.09.001
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发表时间：
2021-12-09
期刊：
影响因子：
23.5
通讯作者：
Caram JR
中科院分区：
文献类型：
--
作者：
Friedman HC;Cosco ED;Atallah TL;Jia S;Sletten EM;Caram JR
合理设计明亮的近短波红外（NIR: 700-1000 SWIR: 1000 - 2000 nm）发射器仍然是一个悬而未决的问题，其应用跨越成像和光子学。结合实验和理论，我们推导出一个能隙量子产率主方程（EQME），描述了有机发色团的SWIR量子产率（ϕF）的基本限制。通过评估21个聚甲基近红外/SWIR发色团的光物理特性来参数化EQME，我们解释了通过与能量间隙相关的高频振动降低辐射率和增加非辐射损失而导致的900 nm以上的ϕ绝对值急剧下降。使用EQME，我们开发了一个与能隙无关的ϕF近红外/SWIR发色团比较度量。我们发现，多甲基杂环上的电子给体特性导致辐射效率的相对增加，但同时红移掩盖了这一点。最后，EQME产生合理的发色团设计见解，通过氘化（由我们的实验结果支持）或分子聚集如何增加SWIR ϕF来显示。近红外和短波红外发射器对于从深层组织成像到光子材料的广泛应用至关重要。然而，有机近红外/SWIR发射器的低量子产率代表了该领域的一个决定性斗争。结合实验和理论，建立了能隙对量子产率的影响模型。通过对该模型的分析和设计一个能隙独立的比较，我们绘制了一个发射率更高的近短波红外染料的路线图。
Rational design of bright near and shortwave infrared (NIR: 700–1000 SWIR: 1000– 2000 nm) emitters remains an open question with applications spanning imaging and photonics. Combining experiment and theory, we derive an energy gap quantum yield master equation (EQME), describing the fundamental limits in SWIR quantum yields (ϕF) for organic chromophores. Evaluating the photophysics of 21 polymethine NIR/SWIR chromophores to parameterize the EQME, we explain the precipitous decline of ϕF past 900 nm through decreasing radiative rates and increasing nonradiative losses via high frequency vibrations relating to the energy gap. Using the EQME we develop an energy gap independent ϕF NIR/SWIR chromophore comparison metric. We show electron donating character on polymethine heterocycles results in relative increases in radiative efficiency obscured by a simultaneous redshift. Finally, the EQME yields rational chromophore design insights shown by how deuteration (backed by our experimental results) or molecular aggregation increases SWIR ϕF. Near and shortwave infrared emitters are vital to a wide range of applications from deep tissue imaging to photonic materials. However, the low quantum yield of organic NIR/SWIR emitters represents a defining struggle in the field. Combining experiment and theory, we model the impact of energy gap on quantum yield. Through analysis of this model and designing an energy gap independent comparison, we created a roadmap to more emissive near and shortwave infrared dyes.
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