Open micro-combinatorial analysis systems of crystal growth critical points of a π-conjugated molecule in ionic liquid nanoliter droplets

Crystal engineering methodologies based on reproducible and high-throughput fabrication of high-quality single crystals have attracted much attention. Crystal formation and growth are governed by crystal growth theory. The driving force of crystallization is systematically represented with phase diagrams. However, constructing phase diagrams usually requires relatively large quantities of samples (milligrams to grams) and substantial time (weeks to months) to evaluate many conditions. Therefore, an easy and quick methodology to obtain phase diagrams, revealing critical conditions for valuable samples, is required. Here, we proposed a new method to obtain phase diagrams based on nanoliter droplet arrays of nonvolatile ionic liquids prepared by inkjet printing. Anthracene derivatives and 1-octyl-4-methylpyridinium derivatives were used as the solute and solvent, respectively. Optimization of ejection conditions, such as applied voltage, frequency, pulse width, and head temperature, enabled the formation of a 0.5 nL droplet per ejection. Inkjet printing under these conditions formed nanodroplet arrays on substrates at a droplet-patterned density of <i>ca.</i> 50 dots per cm². The volume of each patterned droplet was varied from 10 to 100 nL by changing the number of ejections. The dissolution temperature of anthracene at each concentration was obtained at a heating rate of 0.2 °C min^-1. This heating rate was found to be 10 times faster than the conventional technique. The same phase diagram as that prepared by the conventional technique was obtained in the range of 75-300 mM. The standard deviation of the dissolution temperatures was 0.8 °C (2.5%). This technique will facilitate the crystallization of multiple and valuable samples.