Premium
Structural reasons for the formation of multicomponent products and the influence of high pressure
Author(s) -
Konieczny Krzysztof A.,
Bąkowicz Julia,
Paliwoda Damian,
Warren Mark R.,
Ciesielski Arkadiusz,
Cyrański Michał K.,
Turowska-Tyrk Ilona
Publication year - 2021
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
ISSN - 2052-5206
DOI - 10.1107/s2052520621004492
Subject(s) - chemistry , isopropyl , reactivity (psychology) , high pressure , reaction rate , crystal structure , kinetics , crystallography , stereochemistry , medicinal chemistry , organic chemistry , thermodynamics , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics
( 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.