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Article

Structural Transformations in Crystals Induced by Radiation and Pressure. Part 7. Molecular and Crystal Geometries as Factors Deciding about Photochemical Reactivity under Ambient and High Pressures

1
Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland
2
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
*
Authors to whom correspondence should be addressed.
Crystals 2018, 8(7), 299; https://doi.org/10.3390/cryst8070299
Received: 13 June 2018 / Revised: 10 July 2018 / Accepted: 18 July 2018 / Published: 20 July 2018
(This article belongs to the Special Issue Photocrystallography and Solid-State Structural Dynamics)
We studied the photochemical reactivity of salts of 4-(2,4,6-triisopropylbenzoyl)benzoic acid with propane-1,2-diamine (1), methanamine (2), cyclohexanamine (3), and morpholine (4), for compounds (1), (3), and (4) at 0.1 MPa and for compounds (1) and (2) at 1.3 GPa and 1.0 GPa, respectively. The changes in the values of the unit cell parameters after UV irradiation and the values of the intramolecular geometrical parameters indicated the possibility of the occurrence of the Norrish–Yang reaction in the case of all the compounds. The analysis of the intramolecular geometry and free spaces revealed which o-isopropyl group takes part in the reaction. For (1), the same o-isopropyl group should be reactive at ambient and high pressures. In the case of (2), high pressure caused the phase transition from the space group I2/a with one molecule in the asymmetric unit cell to the space group P1¯ with two asymmetric molecules. The analysis of voids indicated that the Norrish–Yang reaction is less probable for one of the two molecules. For the other molecule, the intramolecular geometrical parameters showed that except for the Norrish–Yang reaction, the concurrent reaction leading to the formation of a five-membered ring can also proceed. In (3), both o-isopropyl groups are able to react; however, the bigger volume of a void near 2-isopropyl may be the factor determining the reactivity. For (4), only one o-isopropyl should be reactive. View Full-Text
Keywords: solid-state chemistry; Norrish–Yang reaction; high-pressure crystallography; single-crystal X-ray structure analysis solid-state chemistry; Norrish–Yang reaction; high-pressure crystallography; single-crystal X-ray structure analysis
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MDPI and ACS Style

Konieczny, K.; Ciesielski, A.; Bąkowicz, J.; Galica, T.; Turowska-Tyrk, I. Structural Transformations in Crystals Induced by Radiation and Pressure. Part 7. Molecular and Crystal Geometries as Factors Deciding about Photochemical Reactivity under Ambient and High Pressures. Crystals 2018, 8, 299. https://doi.org/10.3390/cryst8070299

AMA Style

Konieczny K, Ciesielski A, Bąkowicz J, Galica T, Turowska-Tyrk I. Structural Transformations in Crystals Induced by Radiation and Pressure. Part 7. Molecular and Crystal Geometries as Factors Deciding about Photochemical Reactivity under Ambient and High Pressures. Crystals. 2018; 8(7):299. https://doi.org/10.3390/cryst8070299

Chicago/Turabian Style

Konieczny, Krzysztof, Arkadiusz Ciesielski, Julia Bąkowicz, Tomasz Galica, and Ilona Turowska-Tyrk. 2018. "Structural Transformations in Crystals Induced by Radiation and Pressure. Part 7. Molecular and Crystal Geometries as Factors Deciding about Photochemical Reactivity under Ambient and High Pressures" Crystals 8, no. 7: 299. https://doi.org/10.3390/cryst8070299

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