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Competition of Major Forces Dominating the Structures of Porphyrin Assembly

机译：主导卟啉装配结构的主要力量竞争

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Here we take the self-assembly of porphyrin molecules as an example to discover the reason for the diversity of assembled structures. The self-assembly is conducted at a range of pH conditions. Irregular, tubular, and rodlike particles are formed at pH 1.5, 6.5 and 12.5, respectively. X-ray diffraction spectra and UV absorption show that these particles have the same crystalline structures, while the packing types of molecules are different. At low pH, the molecules assemble together by end to end attachment with a J-type aggregation, forming irregular particles. This assembly is dominated by the competition of pi-pi interaction and repulsion force. The latter force is induced by the protonation of molecules under acid conditions. With the increase of pH, the repulsion force is attenuated and finally disappears under basic conditions. The pi-pi interaction becomes the major force under basic conditions, leading to a H-type aggregation via face to face attachment and forming rodlike particles. At the middle pH, the competition disturbs the symmetry of molecules assembly, forming tubular particles. Together with previous studies, we expect that the compromise between competing interactions is probably the governing rule for the diversity of assembled structures.
机译：这里我们以卟啉分子的自组装为例，探讨了组装结构多样性的原因。自组装在一定的pH条件下进行。分别在pH 1.5、6.5和12.5下形成不规则，管状和棒状颗粒。 X射线衍射光谱和UV吸收表明，这些颗粒具有相同的晶体结构，而分子的堆积类型不同。在低pH值下，分子通过J型聚集点对点组装在一起，形成不规则的颗粒。这种组装以pi-pi相互作用和排斥力的竞争为主导。后者的力是由酸性条件下的分子质子化引起的。随着pH的增加，排斥力在碱性条件下减弱并最终消失。 pi-pi相互作用在基本条件下成为主要力量，通过面对面的附着导致H型聚集并形成棒状颗粒。在中等pH值下，竞争干扰了分子组装的对称性，形成了管状颗粒。与以前的研究一起，我们预计竞争相互作用之间的折衷可能是组装结构多样性的支配规则。

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