In‐situ Energy‐Dispersive X‐ray Diffraction Studies of Crystal Growth and Compound Conversion Under Solvothermal Conditions

Abstract

The results of in-situ energy-dispersive X-ray diffraction under solvothermal conditions performed on isostructural, layered thioantimonates Mn 2 Sb 2 S 5 ·L (L = amine) demonstrate the great potential of the method. When the synthesis was carried out at low temperatures with L being 1,3-diaminopropane (DAP), two crystalline intermediate phases were detected which then grew and disappeared when product growth started. Surprisingly, when N-methyl-1,3-diaminopropane (MDAP) was used, no crystalline intermediates could be detected and the induction time was significantly shorter than for DAP. For reactions up to 100°C and for higher temperatures with α Ͻ 0.8 (α is the extent of reaction), the crystallisation is predominantly controlled by nucleation. Further progress of crystallisation (α Ͼ 0.8) leads to a change

Five dimeric thiogermanates with transition metal complexes of multidentate chelating amines: Syntheses, structures, magnetism and photoluminescence

“…The Mn-N bond distances range from 2.227(2) to 2.351(2) Å and the longest Mn1-N1 bond of 2.351(2) Å is trans to the Mn1-S1 bond of 2.472(1) Å ( Table 3). The N-Mn-N bond angles vary between 75.97(8)°and 137.35(9)°, which are comparable with those found in the Mn 2+ complexes coordinated by tren [50][51][52][53]. The axial trans-N1-Mn-S1 bond angle of 174.93(5)°slightly deviates from the ideal value of 180°, indicating a moderate distortion of the polyhedron, which could be further evidenced by the deviations of the axial NMn-N angels from 90°for an ideal geometry.…”

Solvothermal Syntheses of Two New Thiostannates and an In‐Situ Energy Dispersive X‐ray Scattering Study of Their Formation

“…Some selected refinement results are summarized in Table 3. More experimental details can be found in [30,31]. The in-situ investigations were conducted in glass tubes in special autoclaves with an internal diameter of 10 mm and a volume of 7 mL.…”

“…During the last few years we successfully investigated several solvothermal reactions applying time resolved in-situ energy dispersive X-ray diffraction (in-situ EDXRD). [30][31][32][33][34][35][36] This technique facilitates investigations of the influence of different parameters onto the product formation under real reaction conditions. [10,37] The occurrence, growth and decay of crystalline precursors or intermediates can directly be observed which is not possible with ex-situ experiments.…”

The Reaction Mechanism of a Complex Intercalation System: In Situ X‐ray Diffraction Studies of the Chemical and Electrochemical Lithium Intercalation in Cr4TiSe8

“…The experimental set-up, its applicability for in situ EDXRD measurements and the procedures of data treatment were described in detail elsewhere. [36,37] Butyllithium (BuLi) in hexane (2 mL, 1.6 m in hexane) was injected into the tubes through the plug directly before the experiment was carried out. After removal of the cannula, the screw cap was placed on the tube to prevent the plug from being pushed upwards in case of an autogenous pressure in the tube.…”