Kim Hyung Jun, Lee Changhwan, Schuck P James, Kaufman Laura J
Department of Chemistry, Columbia University, New York, NY, 10027, USA.
Department of Chemistry, Massachusetts Institute of Technology (MIT), Cambridge, MA, 02139, USA.
Sci Rep. 2024 Dec 30;14(1):31989. doi: 10.1038/s41598-024-83525-x.
This study characterizes the influence of self-assembly conditions on the aggregation pathway and resulting photophysical properties of one-dimensional aggregates of the simple imide-substituted perylene diimide, N, N'-didodecyl-3,4,9,10-perylenedicarboximide (ddPDI). We show that ddPDI, which has symmetric alkyl chains at the imide positions, assembles into fibers with distinct morphology, emission spectra, and temperature-dependent behavior as a function of preparation conditions. In all conditions explored, aggregates are one-dimensional; however, assembly conditions can bias formation to either J-like or H-like aggregates. Specifically, a solvent phase interfacial (SPI) method yields two types of aggregates with distinct morphology and photophysical properties while a surface and solvent vapor assisted method (SSVA) generates more uniform aggregates with H-dominant behavior. A combined SPI and SSVA approach facilitates the simultaneous generation and in situ characterization of distinct ddPDI assemblies, some of which assemble via seeded growth. Microscopic and spectroscopic imaging unveil the heterogeneity among ddPDI aggregates, each with unique photophysical properties including H-dominant aggregates with a very high degree of molecular alignment and uniformity in intermolecular organization. Overall, this study highlights the pathway complexity in self-assembly of even the simplest PDI molecules, paving the way for utilization of simple PDI aggregates in applications that demand diverse photophysical behavior.
本研究表征了自组装条件对简单的酰亚胺取代苝二酰亚胺N，N'-二十二烷基-3，4，9，10-苝二甲酰亚胺（ddPDI）一维聚集体的聚集途径及由此产生的光物理性质的影响。我们表明，在酰亚胺位置具有对称烷基链的ddPDI，根据制备条件组装成具有不同形态、发射光谱和温度依赖性行为的纤维。在所探索的所有条件下，聚集体都是一维的；然而，组装条件可使聚集体的形成偏向于J型或H型。具体而言，溶剂相界面（SPI）法产生两种具有不同形态和光物理性质的聚集体，而表面和溶剂蒸汽辅助法（SSVA）产生具有H主导行为的更均匀的聚集体。SPI和SSVA相结合的方法有助于同时生成不同的ddPDI组装体并对其进行原位表征，其中一些组装体通过晶种生长进行组装。显微镜和光谱成像揭示了ddPDI聚集体之间的异质性，每个聚集体都具有独特的光物理性质，包括具有非常高的分子排列程度和分子间组织均匀性的H主导聚集体。总体而言，本研究突出了即使是最简单的苝二酰亚胺分子自组装过程中的途径复杂性，为在需要多种光物理行为的应用中利用简单的苝二酰亚胺聚集体铺平了道路。
