The mechanism for the mechanochemical synthesis of (C(NH2 )3 )3 PbI5 3 and (C(NH2 )3 )4 PbI6 4 and their conversion into each other is presented. We investigated the synthesis of 3 at different frequencies and energies using in situ powder X-ray diffraction. By splitting the reaction into single parts we could prove that the formation of 3 is simply dependent on the energy and mixing speed. The nucleation of 4 instead is slightly negative dependent on the energy but dependent on the mixing speed, while its growth is mostly independent of any influence. We were able to influence the reaction pathways by seeding the mixture with a small amount of powdery 4. The formation of 4 is very likely an auto-catalytic process. 3 instead is metastable. It can be stabilized by energy, which beside mechanochemistry can also be achieved by temperature. The results showcases the complex nature of mechanochemical reactions.
Keywords: X-ray diffraction; hybrid composites; mechanochemistry; solid-state reactions.
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