Coordinative Alignment in the Pores of MOFs for the Structural Determination of N-, S-, and P-Containing Organic Compounds Including Complex Chiral Molecules
- 1 November 2019
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 141 (47), 18862-18869
- https://doi.org/10.1021/jacs.9b10501
Abstract
Coordinative alignment of target small molecules onto a chiral metal-organic framework (MOF-520) provides a powerful method to determine the structures of small molecules through single-crystal X-ray diffraction (SXRD). In this work, the structures of seventeen molecules with eight new coordinating functionalities and varying size have been determined by this method, four of which are complex molecules being crystallized for the first time. The chirality of the MOF backbone not only enables enantioselective crystallization of chiral small molecules from a racemic mixture, but also imposes diastereoselective incorporation upon achiral molecules. Crystallographic studies assisted by density functional theory (DFT) calculations indicate that the stereoselectivity of MOF-520 not exclusively comes from the steric confinement of the chiral pore environment but also from asymmetric chemical bonding of the target molecules with the framework that is able to provide sufficient energy difference between possible coordination configurations.Keywords
This publication has 27 references indexed in Scilit:
- X-ray analysis on the nanogram to microgram scale using porous complexesNature, 2013
- A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-PuThe Journal of Chemical Physics, 2010
- OLEX2: a complete structure solution, refinement and analysis programJournal of Applied Crystallography, 2009
- A short history of SHELXActa Crystallographica Section A Foundations of Crystallography, 2007
- Constraints and restraints in refinementPublished by International Union of Crystallography (IUCr) ,2006
- Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracyPhysical Chemistry Chemical Physics, 2005
- Toward reliable density functional methods without adjustable parameters: The PBE0 modelThe Journal of Chemical Physics, 1999
- Protein Hydration Observed by X-ray Diffraction: Solvation Properties of Penicillopepsin and Neuraminidase Crystal StructuresJournal of Molecular Biology, 1994
- Tautomerization of dimethyl phosphonateJournal of the American Chemical Society, 1982
- The Crystal Structure of NaHSO4H2O.Acta Chemica Scandinavica, 1971