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Hybrid organic-inorganic perovskites (HOIPs) occupy a prominent position in the field of materials chemistry due to their attractive optoelectronic properties. While extensive work has been done on the crystalline materials over the past decades, the newly reported glasses formed from HOIPs open up a new avenue for perovskite research with their unique structures and functionalities. Melt-quenching is the predominant route to glass formation; however, the absence of a stable liquid state prior to thermal decomposition precludes this method for most HOIPs. In this work, we describe the first mechanochemically-induced crystal-glass transformation of HOIPs as a rapid, green and efficient approach for producing glasses. The amorphous phase was formed from the crystalline phase within 10 minutes of ball-milling, and exhibited glass transition behaviour as evidenced by thermal analysis techniques. Time-resolved in situ ball-milling with synchrotron powder diffraction was employed to study the microstructural evolution of amorphisation, which showed that the crystallite size reaches a comminution limit before the amorphisation process is complete, indicating that energy may be further accumulated as crystal defects. Total scattering experiments revealed the limited short-range order of amorphous HOIPs, and their optical properties were studied by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Four novel dicyanamide-containing hybrid organic-inorganic ABX 3 structures are reported, and the thermal behaviour of a series of nine perovskite and non-perovskite [AB(N(CN) 2 ) 3 ] (A = (C 3 H 7 ) 4 N, (C 4 H 9 ) 4 N, (C 5 H 11 ) 4 N; B = Co, Fe, Mn) is analyzed. Structure-property relationships are investigated by varying both A-site organic and B-site transition metal cations. In particular, increasing the size of the A-site cation from (C 3 H 7 ) 4 N → (C 4 H 9 ) 4 N → (C 5 H 11 ) 4 N was observed to result in a decrease in T m through an increase in Δ S f . Consistent trends in T m with metal replacement are observed with each A-site cation, with Co < Fe < Mn. The majority of the melts formed were found to recrystallise partially upon cooling, though glasses could be formed through a small degree of organic linker decomposition. Total scattering methods are used to provide a greater understanding of the melting mechanism., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)