Tailored Porphyrin Assembly at the Oil–Aqueous Interface Based on the Receding of Three‐Phase Contact Line of Droplet Template

Abstract

a wide variety of nanoparticles in designed arrays via guiding TCL based on micropillar strategy. [ 4e,f ] Previous studies have enabled to precisely manipulate micro-, nanoparticles or even small molecules into well-defi ned patterns through fl exibly designing of TCL. However, there still remains a challenge to engineer moleculescale assembly by TCL owing to the difficulty in the well-ordered arrangement of molecular structure. Just recently, Baram et al. [ 6 ] demonstrated a single-crystal assembly by varying the receding behavior of TCL via using hydrophobic substrate. Porphyrin assemblies [9][10][11][12][13][14] with well-defi ned morphologies and aggregate modes are important for the optic-electric properties. Especially, J-aggregates are one kind of typical porphyrin aggregate, which affects greatly the resultant performance. They are formed with the monomeric molecules arranged in 1D such that the transition moment of the monomers is parallel and the angle between the transition moment and the line joining the molecular centers is zero (ideal case). [ 10a , b , 13 ] Herein, we achieved a well-designed porphyrin assembly on both molecule aggregate state and aggregate morphology by adjustable TCL of droplet template via constructing an oilaqueous interface. In our system, aggregate morphologies are controlled from the water droplet template, [ 7,8 ] while the aggregate mode referring to the orientated arrangement of amphiphilic porphyrin molecule is realized by oil-water interface. As a result, a tailored porphyrin assembly can be achieved by varying the sliding behavior of TCL of water droplet template that is realized by modulating the hysteresis behavior of substrate or solvent ratios of porphyrin dispersion. Not only the assembled morphologies of porphyrin aggregate can be modulated from ring-, wheel-, to hole-shell or even more delicate topological structures, the aggregate modes of porphyrin molecules were tuned from various nonspecifi c J-like-to-J-like aggregate. Furthermore, a transition from noncrystals-to-crystal state occurs to the porphyrin assembly in this process. This modulation was mainly attributed to the fi ne tune of sliding TCL at the oilwater interface, which greatly contributed to the well-ordered molecule assembly owing to the prolonging assembly time and enhanced assembly interaction. This work will open a new venue for the design and creation of novel porphyrin structures and is of especial signifi cance for the potential applications in optic devices.A novel and robust approach to controllable porphyrin assembly is developed at the oil-aqueous interface by tuning the receding of three-phase contact line of droplet template. The assembled morphologies (ring-, wheel-, and hole-shell shape), aggregate modes and crystal states of porphyrin molecules can be effectively tailored by modulating the receding behavior of threephase contact line, which can be realized by varying the hysteresis behavior of substrate or solvent ratios. The developed method for tailored porphyrin assembly w...

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