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

DOI: 10.1107/S2052520621004492 DOI Help

Authors: Krzysztof Konieczny (Wrocław University of Science and Technology) , Julia Bąkowicz (Wrocław University of Science and Technology) , Damian Paliwoda (ICGM, Université de Montpellier, CNRS, ENSCM) , Mark R. Warren (Diamond Light Source) , Arkadiusz Ciesielski (University of Warsaw) , Michał K. Cyrański (University of Warsaw) , Ilona Turowska-Tyrk (Wrocław University of Science and Technology)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Acta Crystallographica Section B Structural Science, Crystal Engineering And Materials , VOL 77 , PAGES 321 - 330

State: Published (Approved)
Published: June 2021
Diamond Proposal Number(s): 23404

Abstract: (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.

Journal Keywords: crystal structure; high-pressure structure; photochemistry; X-ray structure analysis; solid-state reaction

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Discipline Tags:

Organic Chemistry Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)