Assessment of an Effective Quasirelativistic Methodology Designed to Study Astatine Chemistry

Mapping of the interaction sites of galanthamine: a quantitative analysis through pairwise potentials and quantum chemistry

Nicolas Galland, Soleymane Kone and Jean-Yves Le Questel*

Electronic Supplementary Material

Section 1. Movies

Movie 1 entitled “ax1-H2O_long.avi” displays the result predicted by the MP2fit/DMA calculations between a water molecule and GALw (the N-methyl substituent in the GAL subfragment is in axial position and the GAL subfragment exhibits an intramolecular O15H16…O4 HB) for a long-range approach. The stability of the formed complex results from the interaction between the free water molecule and the water molecule belonging to GALw (partial neutralization of N11H+).

Movie 2 entitled “ax2-O15-O4-O13_short.avi” displays the result predicted by the MP2fit/DMA calculations between a water molecule and GALw (the N-methyl substituent in the GAL subfragment is in axial position and the O15H grouphas a trans orientation with respect to the C5-C6 bond) for a short-range approach. The originality of the formed complex results from the multicentred HB interactions between the free water molecule and the oxygen atoms belonging to the GAL subfragment.

Section 2. Tables

Table S1.Proportions(%) of GALw+H2O complexesyielded by the MP2fit/DMA calculations as a function of (i) the nature of the interactions and (ii) the intermolecular approach between the monomers.

aIn the xnnotation: x denotes the position (ax/eq) of the N-methyl substituent in the GAL subfragment; n denotes the conformation of the GAL subfragment with: intramolecular O15H16…O4 HB (1), a trans orientation of the O15H group with respect to the C5-C6 bond (2), a gauche orientation of the O15H group with respect to the C5-C6 bond (3).bDenotes the GALw sites involved in the interaction with the water molecule.

Table S2.Proportions(%) of GALw+C6H6 complexesyielded by the MP2fit/DMA calculations as a function of (i) the nature of the interactions and (ii) the intermolecular approach between the monomers.

aIn the xnnotation: x denotes the position (ax/eq) of the N-methyl substituent in the GAL subfragment; n denotes the conformation of the GAL subfragment with: intramolecular O15H16…O4 HB (1), a trans orientation of the O15H group with respect to the C5-C6 bond (2), a gauche orientation of the O15H group with respect to the C5-C6 bond (3). bDenotes the GALw sites involved in the interaction with the benzene molecule.

Table S3.Recurrence (%) of the various intermolecular interactions in the GALw+2H2O complexesyielded by the MP2fit/DMA calculations.

aDenotes the GALw sites involved in the interaction with the water molecules.bIn the xnnotation: x denotes the position (ax/eq) of the N-methyl substituent in the GAL subfragment; n denotes the conformation of the GAL subfragment with: intramolecular O15H16…O4 HB (1), a trans orientation of the O15H group with respect to the C5-C6 bond (2), a gauche orientation of the O15H group with respect to the C5-C6 bond (3).

Table S4. Recurrence (%) of the various intermolecular interactions in the GALw+C6H6+H2O complexesyielded by the MP2fit/DMA calculations.

aDenotes the GALw sites involved in the interaction with the water/benzene molecule.bIn the xnnotation: x denotes the position (ax/eq) of the N-methyl substituent in the GAL subfragment; n denotes the conformation of the GAL subfragment with: intramolecular O15H16…O4 HB (1), a trans orientation of the O15H group with respect to the C5-C6 bond (2), a gauche orientation of the O15H group with respect to the C5-C6 bond (3).cAmountfor the water/benzene molecule involved in the specified interaction with GALw.

Table S5.Decomposition ofthe interaction energy for the most significant GALw+2H2O complexes. First aregiven thevalue (kJ/mol) computed at LMP2 level of theory, followed in italic characters by the ones computed at MPWB1Klevel of theory.a

Complexb

aThe complexes are formed from A (GALw), B (water) and C (water) monomers.bIn the xn:i:j notations: x denotes the position (ax/eq) of the N-methyl substituent in the GAL subfragment; n denotes the conformation of the GAL subfragment with : intramolecular O15H16…O4 HB (1), a trans orientation of the O15H group with respect to the C5-C6 bond (2), a gauche orientation of the O15H group with respect to the C5-C6 bond (3); i and j denote the GALw sites involved in the interaction with the two water molecules.

Table S6. Decomposition of the interaction energy for the most significant GALw+C6H6+H2O complexes. First aregiven the value (kJ/mol) computed at LMP2 level of theory, followed in italic characters by the ones computed at MPWB1Klevel of theory.a

Complexb

aThe complexes are formed from A (GALw), B (water) and C (benzene) monomers.bIn the xn:i:j notations: x denotes the position (ax/eq) of the N-methyl substituent in the GAL subfragment; n denotes the conformation of the GAL subfragment with : intramolecular O15H16…O4 HB (1), a trans orientation of the O15H group with respect to the C5-C6 bond (2), a gauche orientation of the O15H group with respect to the C5-C6 bond (3); idenotes the GALw site involved in the interaction with the water molecule; j denotes the GALw site involved in the interaction with the benzene molecule.

Section 3. Optimized structures

The geometries computed at MPWB1K/6-31+G(d,p) level of theory are reported for the GALw+H2O, GALw+C6H6, GALw+2H2Oand GALw+C6H6+H2Osystems.The atomic numbers are given first followed by the three atomic cartesian coordinates in Angstrom.

GALw+H2O system

GALw+C6H6 system

GALw+2H2O system

GALw+C6H6+H2O system