Hydrophobicity directed guest-inclusion for structure-elucidation of enclatherated guests within a crystalline sponge by SC-XRD

• Published in: Journal of molecular structure 2022-03, Vol.1251, p.132054, Article 132054
• Main Authors: Chauhan, Pratibha, Javed, Saleem, Levendis, Demetrius C., Fernandes, Manuel
• Format: Article
• Language: English
• Subjects: Effect of polarity on guest encapsulation in MOF; Hirshfeld surfaces & Fingerprint plot calculation for guest-host noncovalent interactions; Molecular Structure determination by crystalline sponge method; Non-crystalline state crystallography; Postcrystallization in MOF; Recognition sites in Zn-TPT MOF; Relative impact of side groups functionality on guest occupancy; Solvent optimization for guest soaking in MOF
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2021.132054

•Analogous dithiines, were post crystallized to be characterized by SCXRD within MOF.•The relative impact on guest-occupancy and recognition site within MOF was studied.•Hirshfeld surface with fingerprint plot analysis was performed for interactions.•The study is a clue for the successful structure determination without crystallization. The synergic role of hydrophobicity and H-bonding for guest-insertion, and its sustenance within sponge-voids, was explained through structure-elucidation of comparative guest molecules. Guest dithiin-compounds with varying side groups’ functionalities paved a way to investigate a guest-host binding mechanism. Along with structure characterization, hydrophobic, hydrogen bonding, and other n…π*, n…σ*, and CH…π, interactions in the host-guest complexes, were also quantified by fingerprint plot analysis of hirshfeld surfaces, for the recognizance of predominant interactions, responsible for successful guest-host coordination. The guest-compounds, of nearly similar characteristics, occupied the same void space with almost similar orientation in a host-framework in centrosymmetric space group. However, the chemical and physical characteristics of the side groups influenced the absorption or guest-occupancy in MOF to the great extent. Two distinct molecular-recognition sites were noticed for solvent and guest molecules within a sponge. [Display omitted]