SUPPORTING INFORMATION

Size: px

Start display at page:

Download "SUPPORTING INFORMATION"

Pamela McBride
5 years ago
Views:

1 SUPPORTING INFORMATION Self-Assembly of Fluorinated Boronic Esters and 4,4 -Bipyridine into 2:1 N B Adducts and Inclusion of Aromatic Guest Molecules in the Solid State: Application for the Separation of o,m,p Xylene Gonzalo Campillo-Alvarado,,,# Eva C. Vargas-Olvera,,# Herbert Ho pfl,*, Angel D. Herrera-Espan a, Obdulia Sa nchez-guadarrama, Hugo Morales-Rojas,*, Leonard R. MacGillivray, Braulio Rodríguez-Molina, and Norberto Farfa n Centro de Investigaciones Químicas, Instituto de Investigacio n en Ciencias Ba sicas y Aplicadas, Universidad Auto noma del Estado de Morelos, Av. Universidad 1001, Chamilpa, Cuernavaca 62209, Morelos, Me xico Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States Instituto de Química and Facultad de Química, Departamento de Química Orga nica, Universidad Nacional Auto noma de Me xico, Ciudad de Me xico 04510, Me xico List of contents 1. IR spectra for A1 A5 (Fig. S1 S5). 2. Experimental and simulated PXRD patterns for A1 A5 (Fig. S6 S10). 3. Experimental setup for the preparation of A3 using liquid-assisted grinding (Fig. S11). 4. Perspective views of the molecular structures of A1 A5 (Fig. S12). 5. Perspective views of fragments of the crystal structures of AA5 (Fig. S13). 6. IR spectra, experimental and simulated PXRD patterns and TG graphs for the inclusion complexes (Fig. S14-S38). 7. Perspective view of a fragment of the crystal structure of A3 BrPOH (Fig. S39) H NMR spectra recorded during the xylene isomer separation experiments (Fig. S40). 9. Tables with complementary geometric data including intermolecular interactions for the crystal structures of the compounds studied herein (Table S1-S5). 10. Data from the TGA/DSC analysis for adducts A1 A5 and the inclusion compounds studied herein (Table S6). 11. Illustration of the procedure for the enrichment of o-xylene in the solid state structure of A3 xylene (Scheme S1).

2 Figure S1. FTIR spectra of A1 and starting materials. Figure S2. FTIR spectra of A2 and starting materials. Figure S3. FTIR spectra of A3 and starting materials.

3 Figure S4. FTIR spectra of A4 and starting materials. Figure S5. FTIR spectra of A5 and starting materials.

4 A1 simulated A1 bpy 2H 2 O simulated bpy simulated phbe Figure S6. Experimental and simulated PXRD pattern of A1 in comparison to the starting materials. A2 simulated A2 bpy 2H 2 O simulated bpy simulated 4fphbe Figure S7. Experimental and simulated PXRD pattern of A2 in comparison to the starting materials.

5 A3 simulated A3 bpy 2H 2 O simulated bpy simulated 24fphbe Figure S8. Experimental and simulated PXRD pattern of A3 in comparison to the starting materials. A4 simulated A4 bpy 2H 2 O simulated bpy simulated 246fphbe Figure S9. Experimental and simulated PXRD pattern of A4 in comparison to the starting materials.

Preparation of A3 by liquid-assisted grinding of the starting materials (i.e. the catechol ester of 2,4-difluorophenylboronic acid and 4,4 -bipyridine).

6 A5 simulated A5 bpy 2H 2 O simulated bpy simulated cat pfphba Figure S10. Experimental and simulated PXRD pattern of A5 in comparison to the starting materials. Figure S11. Preparation of A3 by liquid-assisted grinding of the starting materials (i.e. the catechol ester of 2,4-difluorophenylboronic acid and 4,4 -bipyridine). Formation of the boronate ester adduct is indicated by the color change.

7 Figure S12. Perspective views of the molecular structures of a) A1, b) A2, c) A3, d) A4 and e) A5. Ellipsoids are drawn at the 50% probability level. Figure S13. Similar to A1, the crystal structures of AA5 exhibit 2D layers with herringbone-type patterns: a) A2, b) A3, c) A4, and d) A5. Note: For clarity, only hydrogen atoms involved in intermolecular contacts are shown.

8 Figure S14. FTIR spectra of A3 BEN. Figure S15. FTIR spectra of A3 TOL. Figure S16. FTIR spectra of A3 mxyl

9 ṽ C-O Figure S17. FTIR spectra of A3 pxyl Figure S18. FTIR spectra of A3 ANI. Figure S19. FTIR spectra of A3 NAP.

10 ṽ C-O Figure S20. FTIR spectra of A3 oxyl ṽ C-O Figure S21. FTIR spectra of A3 BENCN. Figure S22. FTIR spectra of A3 MES.

11 Figure S23. FTIR spectra of A3 NAPOH. Figure S24. FTIR spectra of A3 BrPOH

12 Figure S25. PXRD patterns for crystalline samples of A3 BEN, A3 TOL, A3 mxyl, A3 pxyl, A3 ANI, A3 NAP, A3 oxyl, A3 BENCN, A3 MES, A3 NAPOH, A3 BrPOH and A3 TTF MES.

13 A3 BEN A3 BEN simulated Figure S26. Experimental and simulated PXRD pattern of A3 BEN. A3 TOL A3 TOL simulated Figure S27. Experimental and simulated PXRD pattern of A3 TOL.

14 A3 mxyl A3 mxyl simulated Figure S28. Experimental and simulated PXRD pattern of A3 mxyl. A3 pxyl A3 pxyl simulated Figure S29. Experimental and simulated PXRD pattern of A3 pxyl.

15 A3 ANI A3 ANI simulated Figure S30. Experimental and simulated PXRD pattern of A3 ANI. A3 NAP A3 NAP simulated Figure S31. Experimental and simulated PXRD pattern of A3 NAP.

16 A3 oxyl A3 oxyl simulated Figure S32. Experimental and simulated PXRD pattern of A3 oxyl. A3 BENCN A3 BENCN simulated Figure S33. Experimental and simulated PXRD pattern of A3 BENCN.

17 A3 MES A3 MES simulated Figure S34. Experimental PXRD pattern of A3 MES. A3 NAPOH A3 NAPOH simulated Figure S35. Experimental and simulated PXRD pattern of A3 NAPOH.

18 A3 BrPOH A3 BrPOH simulated Figure S36. Experimental and simulated PXRD pattern of A3 BrPOH.

19 Weight (%) Weight (%) 100 Weight (%) Weight (%) Weight (%) % 100% 100% 100% A5 A4 A3 A % A Temperature ( C) Figure S37. Thermogravimetric analysis for adducts A1-A5 with the correspondent weight lost.

20 Weight (%) Weight (%) Weight (%) Weight (%) Weight (%) Weight (%) Weight (%) Weight (%) Weight (%) A3 BrPOH A3 NAPOH A3 BENCN A3 ANI A3 MES A3 NAP A3 TOL A3 BEN A Temperature ( C) Fig S38. Thermogravimetric analysis for inclusion compounds with adduct A3.

21 Figure S39. Perspective view of a fragment of the crystal structure of A3 BrPOH showing the structural relationship with A3 NAPOH.

22 Fig. S40. 1 H NMR spectra recorded during the xylene isomer separation experiments.

23 Table S1. Geometries for intermolecular contacts in the crystal structures of A1-A5. Intralayer contacts Interlayer contacts distance (centroid centroid) [Å] Shortest contact [Å] Angle mean planes arylb py [ ] C H O C H C H F C H C H F A1 [a] (2) , 3.333(2); Cg1(N1,C13 C17) Cg2(C7 C12) i C8 C15 ii C16 H16 O2 i A2 [b] (2) , 3.358(2); Cg1(N1,C13 C17) Cg2(C1 C6) i C6 C15 ii C14 H14 O2 i , 3.410(2); C3 H3 C8 iii , 3.479(3); C9 H9 C5 iii , 3.446(3); C5 H5 F1 iv A3 [c] (2) , 3.381(3); Cg1(N2,C30 C34) Cg2(C13 C18) i C14 C31 iii C1H1 O4 v (2) , 3.180(2); Cg3(N1,C25 C29) Cg4(C1 C6) ii C C26 iv C31 H31 O3 i 2.50, 3.339(2); C33 H33 O2 ii A4 [d] (2) , 3.451(2); Cg1(N17,C30 C34) Cg2(C13 C18) i C14 C31 iii C21 H21 O1 v (2) , 3.211(2); Cg3(N13,C25 C29) Cg4(C1 C6) ii C C26 iv C26 H26 O2 ii 2.45, 3.298(2); C28 H28 O3 i 2.74, 3.606(3); C3 H3 C12 iv 2.77, 3.664(2); C3 H3 C12 iv 2.68, 3.566(2); C15 H15 C21 iii , 3.122(2); C28 H28 F2 vi , 3.107(2); C33 H33 F5 vi A5 [e],[f] , 3.592(6); , 3.502(7); , 3.266(7); , 2.936(6); C16 H16 O1 i C14 H14 C7 ii C9 H9 F5 iii C13 H13 F4 iv 2.62, 3.207(6); C16 H16 F1 i 2.56, 3.001(7); C17 H17 F3 v [a] Symmetry operators: (i) x, ½-y, -½+z; (ii) x, ½-y, ½+z; (iii) -1+x, y, z. [b] (i) x, ½-y, ½+z; (ii) x, ½-y, -½+z; (iii) 1+x, y, z; (iv) x, 1-y, -z. [c] (i) 1-x, ½+y, ½-z; (ii) 2-x, -½+y, ½-z; (iii) 1-x, -½+y, ½-z; (iv) 2-x, ½+y, ½-z; (v) 1+x, y, z; (vi) x, ½-y, ½+z. [d] (i) -x, ½+y, ½-z; (ii) 1-x, -½+y, ½-z; (iii) -x, -½+y, ½-z; (iv) 1-x, ½+y, ½-z; (v) -1+x, y, z; (vi) x, ½-y, -½+z;. [e] (i) -½+x, ½-y, -½+z; (ii) ½-x, -½+y, 1½-z; (iii) -x, 1-y, 1- z; (iv) -½+x, ½-y, ½+z; (v) 1+x, y, z. [f] Contrary to the remaining structures, in A5 neighboring adduct molecules are located alternately above and below the 2D layer mean plane, which causes that with exception of C17 H17 F3 all contacts are located both in the intra- and interlayer connectivity zone.

24 Table S2. Selected geometric parameters for the description of the molecular structures of A3, A3 BEN, A3 TOL and A3 ANI. N B (Å) 1.664(2) 1.660(3) B O (Å) 1.470(2) 1.468(2) 1.468(2) 1.467(2) B C (Å) 1.595(3) 1.598(3) O B O ( ) 106.9(1) 107.2(1) Boron THC (%) A3 A3 BEN A3 TOL A3 ANI 1.663(2) 1.665(5) 1.661(3) 1.466(2) 1.474(2) 1.460(5) 1.496(5) 1.480(3) 1.463(3) 1.592(2) 1.572(6) 1.589(3) (13) 105.5(3) (18) B B (Å) aryl B cat (Å) [a] Angles between mean planes (º) [b] py,py (º) cat,cat (º) aryl B,aryl B (º) py (º) cat (º) aryl (º) py,cat (º) py,aryl (º) cat,aryl (º) Torsion angles along B B axis (º) [c] aryl B B1 B1 /B2 aryl B cat B1 B1 /B2 aryl B cat B1 B1 /B2 cat [a] Distance between the centroids of opposite B-aryl substituents (aryl B) and catecholate (cat) rings along the long N N molecular axis. [b] The mean planes refer to the individual pyridyl rings (py) within bpy, the aromatic ring of the catecholate fragment (cat) and the aromatic ring of the B-aryl substituent (aryl B). py, cat and aryl are the angles formed between the mean planes of the aromatic rings in the adduct, which are reported in relation to a reference plane defined by the N, B and C i atoms. py,cat py,aryl and cat,aryl are the angles at the intersection of straight lines formed between the boron atom and the centroids of the respective aromatic rings. [c] Aryl B and cat represent the centroids of the catecholate and B-aryl substituents, respectively. B1 and B1 /B2 correspond to the boron atoms in the molecular structure.

25 Table S3. Geometries for intermolecular contacts in the crystal structures of A3 BEN, A3 TOL and A3 ANI. Intermolecular host-guest contacts Intermolecular host-host contacts distance (centroid centroid) [Å] distance (mean plane bpy centroid guest [Å] Angle mean planes guest bpy [ ] C H F C H O C H C H F A3 BEN [a] , 3.327(3); Cg2(C31 C33, C31 i -C33 i ) Cg1(N1,C13 C17) C3H3 F1A 2.68, 3.348(2); C3 H3 O2 ii 2.64, 3.533(3); C17 H17 C11 iii 2.46, 3.342(2); C13 H13 F2 iv 2.62, 3.238(3); C33 H33 F1A A3 TOL [b] , 3.15(1); Cg1(C31 C36) Cg2(N1,C13A C17A) i C37 H37A F1B 2.69, 3.415(5); C5 H5 O2 ii 2.78, 3.56(1); C17 H17 C11 iii 2.41, 3.33(2); C13 H13A F2 vi , 3.15(1); Cg3(C31 C36) Cg4(N1,C13A C17A) C37 H37C F1B A3 ANI [c] , 3.103(8); Cg1(C31 C36) Cg2(N1,C13 C17) i N31 H31B F1A 2.70, 3.397(3); C3 H3 O1 iv 2.65, 3.532(4); C13 H13 C10 v 2.59, 3.195(3); C1H1 F1A vi , 2.883(6); Cg3(C31 C36) Cg4(N1,C13 C17) C33 H33 ii F1A iii 2.47, 3.366(3); C17 H17 F2 vii 2.29, 3.033(6); C34 H34 F1A iii [a] Symmetry operators: (i) -x, -y, 1-z; (ii) -1+x, y, z; (iii) x, ½-y, ½+z; (iv) -x, -½+y, ½-z. [b] (i) -x, 1-y, -z; (ii) 1+x, y, z; (iii) x, 1½-y, -½+z; (iv) 1-x, -½+y, ½-z. [c] (i) 1-x, 1-y, 2-z; (ii) x, y, 1+z; (iii) -x, 1-y, 2-z; (iv) -1+x, y, z; (v) x, ½-y, ½+z; (vi) 1+x, y, z; (vii) x, ½+y, 1½-z.

26 Table S4. Selected geometric parameters for the description of the molecular structures of A3, A3 oxyl, A3 BENCN, A3 NAPOH, A3 BrPOH and A3 TTF MES. A3 A3 oxyl A3 BENCN A3 NAPOH A3 BrPOH A3 TTF MES N B (Å) 1.664(2) 1.660(3) B O (Å) 1.470(2) 1.468(2) 1.468(2) 1.467(2) (17) 1.635(4) 1.631(4) (17) (17) 1.468(4) 1.473(4) 1.467(4) 1.468(4) 1.661(3) 1.663(3) 1.642(4) 1.466(2) (19) 1.462(3) 1.481(3) 1.471(4) 1.477(4) B C (Å) 1.595(3) 1.598(3) O B O ( ) 106.9(1) 107.2(1) Boron THC (%) (19) 1.606(5) 1.612(5) (10) 106.5(3) 106.9(3) B B (Å) aryl B cat (Å) [a] (2) 1.599(3) 1.613(4) (12) (18) 106.6(2) Angles between mean planes (º) [b] py,py (º) cat,cat (º) aryl,aryl (º) py (º) cat (º) aryl (º) py,cat (º) py,aryl (º) cat,aryl (º) Torsion angles along B B axis (º) [c] aryl B1 B1 /B2 aryl cat B1 B1/B2 aryl B cat B1 B1 /B2 cat [a] Distance between the centroids of opposite B-aryl substituents (aryl) and catecholate (cat) rings along the long N N molecular axis. [b] The mean planes refer to the individual pyridyl rings (py) within bpy, the aromatic ring of the catecholate fragment (cat) and the aromatic ring of the B-aryl substituent (aryl). py, cat and aryl are the angles formed between the mean planes of the aromatic rings in the adduct, and the reference plane defined by the N, B and C i atoms. py,cat py,aryl and cat,aryl are the angles at the intersection of straight lines formed between the boron atom and the centroids of the respective aromatic rings. [c] Aryl and cat represent the centroids of the catecholate and B-aryl substituents, respectively. B1 and B1 /B2 correspond to the boron atoms in the molecular structure.

27 Table S5. Geometries for intermolecular contacts in the crystal structures of A3 oxyl, A3 BENCN, A3 NAPOH, A3 BrPOH and A3 TTF MES. Intermolecular host-guest contacts Intermolecular host-host contacts distance (centroid centroid) [Å] distance (mean plane bpy centroid guest [Å] Angle mean planes guest bpy [ ] C H F C H X H Y (X = C, O; Y = O, N) C H O C H C H F A3 oxyl [a] 3.67 Cg1(C31 C36) Cg2(N1,C13 C17) , 3.200(2); C35 H35 F2 i 2.79, 3.652; C36 H36 Cg(C7-C12) , 3.268(1); C17 H17 O2 iii , 3.537(2); C3 H3 F2 iv 2.75, 3.680(4); , 3.285(2); C38 H38B F1A ii C1H1 F2 v A3 BENCN [b] 3.86 Cg1(C35 C40) i Cg2(N1,C13 C17) , 3.433; C38 H38 Cg5(C7-C12) ii 2.72, 3.443(6); C6 H6 N3 iii 2.31, 3.126(5); C13 H13 O1 vii , 3.575(5); C27 H27 F2 xi , 3.386; Cg3(C4C47) Cg4(N1,C30 C34) C45 H45 Cg6(C24-C29) 2.68, 3.593(8); C9 H9 N3 2.63, 3.115(5); C17 H17 O2 viii 2.59, 3.460(6); C1H1 N3 iv 2.58, 3.078(5); C30 H30 O3 ix 2.71, 3.452(8); C23 H23 N4 v 2.29, 3.113(4); C34 H34 O4 x 2.66, 3.520(6); C26 H26 N4 vi 2.65, 3.565(7); C29 H29 N4 ii A3 NAPOH [c] , 3.469(2); Cg1(C2C27) i Cg2(N1,C13 C17) C19 H19 F1 iii , 3.177(2); Cg3(C18 C23) Cg4(N1,C13 C17) ii C27 H27 F2 iv 2.62, 3.520; C25 H25 Cg5(C7-C12) v 1.96, 2.763(2); O3 H3A O2 2.57, 3.250(2); C6 H6 O3 vi , 3.641(2); C3 H3 C12 vii A3 BrPOH [d] , 3.469(2); Cg1(C31 C36) Cg2(N1,C13 C17) C36 H36 F2 i 2.87, 3.705; C34 H34 Cg3(C7-C12) 1.96, 2.770(2); , 3.474(2); O31 H31 O2 ii C14 H14 F1 ii 2.69, 3.394(3); C6 H6 O31 iii A3 TTF MES [e],[f] , 3.414(4); Cg1(S1,S2,C18 C20) Cg2(N1,C13 C17) C2H2 F2 ii 2.62, 3.406; C19 H19 Cg5(C1-C6) , 3.303(4); C17 H17 O2 iv , 3.438; , 3.475(4); Cg1(S3,S4,C21 C23) Cg2(N1,C13 C17) i C23 H23 Cg6(C7-C12) i C31 H31C O2 v 2.73, 3.640(5); , 3.410(5); C20 H20 C27 iii C3H32A O1 vi [a] Symmetry operators: (i) -x, 2-y, 1-z; (ii) -x, 1-y, 1-z; (iii) 1-x, 1-y, 1-z; (iv) -x, 2-y, 2-z; (v) x, y, -1+z. [b] (i) x, -1+y, z; (ii) (ii) x, 1+y, z; (iii) 1-x, -y, -z; (iv) 1+x, y, z; (v) 1-x, -y, 1-z; (vi) 1+x, 1+y, z; (vii) 2-x, -y, -z; (viii) 1-x, -y, -z; (ix) 1-x, 1-y, 1-z; (x) 2-x, 1-y, 1-z; (xi) 2- x, 1-y, -z. [c] (i) -½+x, ½-y, -½+z; (ii) -x, 1-y, -z; (iii) ½-x, ½+y, ½-z; (iv) 1-x, -y, 1-z; (v) ½+x, ½-y, ½+½z; (vi) ½-x, ½-y, ½+z; (vii) ½-x, ½+y, ½-z. [d] (i) 1½-x, -½+y, 1½-z; (ii) -½+x, 1½-y, -½+z; (iii) 1-x, 2-y, 1-z. [e] (i) 1-x, 2-y, -z; (ii) 1-x, 1-y, -z; (iii) 1-x, 1-y, 1-z; (iv) 2-x, 2-y, -z; (v) 1+x, -1+y, z; (vi) x, -1+y, z. [f] In this case the interactions with mesitylene are registered within the host host interactions.

28 Table S6. Selected information from the TGA/DSC analysis for adducts A1 A5 and the inclusion compounds studied herein. Adduct Adduct/ Guest ratio Boiling Point guest [ C] Onset temp [ C] Peak temp [ C] % Weight loss (exp./calcd.) Thermal process A1 1: /100 Adduct elimination A2 1: /100 Adduct elimination A3 1: /100 Adduct elimination A4 1: /100 Adduct elimination A5 1: /100 Adduct elimination A3 BEN 1: /11.2 Guest evaporation /88.8 Adduct elimination A3 TOL 1: /12.9 Guest evaporation /87.1 Adduct elimination A3 oxyl 1: /25.5 Guest evaporation /74.5 Adduct elimination A3 mxyl 1: /14.6 Guest evaporation /85.4 Adduct elimination A3 pxyl 1: /14.6 Guest evaporation /85.4 Adduct elimination A3 MES 1: /16.2 Guest evaporation /83.8 Adduct elimination A3 NAP 1: /100 Guest evaporation + Adduct elimination A3 ANI 1: /100 Guest evaporation + Adduct elimination A3 BENCN 1: /25.0 Guest evaporation /75.0 Adduct elimination A3 NAPOH 1: /100 Guest evaporation Adduct elimination A3 BrPOH 1: /35.8 Guest evaporation /64.2 Adduct elimination

29 Scheme S1. Illustration of the procedure for the enrichment of o-xylene in the solid state structure of A3 xylene. (1) Preparation of a o,m,p-xylene solution in 1:1:1 stoichiometry, (2) addition of molecular components for the formation of A3, (3) inclusion complex formation by self-assembly, (4) crystal separation and 1 H NMR measurement of the xylene ratio.

Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 106 parameters 2 restraints

Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 106 parameters 2 restraints organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 2,4-Difluorophenylboronic acid Patricia Rodríguez-Cuamatzi, a Hugo Tlahuext b and Herbert Höpfl b * a Universidad