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Structural reasons for the formation of multicomponent products and the influence of high pressure

Autor
R, Warren Mark
Damian, Paliwoda
TUROWSKA-TYRK, ILONA
BĄKOWICZ, JULIA
KONIECZNY, KRZYSZTOF
Cyrański, Michał
Ciesielski, Arkadiusz
Data publikacji
2021
Abstrakt (EN)

(S)-(−)-1-Phenyl­ethan­aminium 4-(2,4,6-tri­iso­propyl­benzoyl)­benzoate (S-PEAT­PBB) undergoes a photochemical reaction in its crystalline form upon UV irradiation and forms three different products: the first product is the result of a Yang cyclization with the participation of the δ-H atom of o-iso­propyl (product D) and the second and third products are obtained via a Norrish–Yang reaction with the involvement of the γ-H atom of 2-iso­propyl (product P) and 6-iso­propyl (product Z). These products are formed in different proportions (D > P >> Z). The path and kinetics of the reaction were monitored step-by-step using crystallographic methods, both under ambient and high-pressure conditions. The reactivity of S-PEATPBB depends strongly on the geometry of the reaction centre and the volume of the reaction cavity. Due to the geometrical preferences making the cyclization reaction easier to proceed, product D dominates over the other products, while the formation of product Z becomes difficult or almost impossible at high pressure. The reaction proceeds with an increase of the unit-cell volume, which, suppressed by high pressure, results in a significant decrease of the reaction rate. The crystal lattice of S-PEATPBB shows high elasticity. The quality of the partially reacted crystal remains the same after decom­pression from 0.75 GPa to 0.1 MPa.

Słowa kluczowe EN
crystal structure
high-pressure structure
photochemistry
X-ray structure analysis
solid-state reaction
Dyscyplina PBN
nauki chemiczne
Czasopismo
Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
Tom
B77
Zeszyt
pt. 3
Strony od-do
321-330
ISSN
2052-5206
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