Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal-Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission

Transcription

1 Phenyl Ring Dynamics in a Tetraphenylethylene-Bridged Metal-Organic Framework: Implications for the Mechanism of Aggregation-Induced Emission Natalia B. Shustova, Ta-Chung Ong,, Anthony F. Cozzolino, Vladimir K. Michaelis,, Robert G. Griffin,, * and Mircea Dincă * Department of Chemistry, Massachusetts Institute of Technology Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology Cambridge, Massachusetts, USA, Supporting Information Table of Contents Page Number Table S1. X-ray crystal structure refinement data for TPE-d 20, 1a, and 1b at various temperatures S3 Figure S1. Thermogravimetric analysis plots for 1 and 1H S4 Figure S2. Simulated and experimental PXRD patterns of 1c S5 Figure S3. VT 1 H NMR spectra of TPE and H 4 TPEC in CD 2 Cl 2 and CD 3 OD S6 Table S2. The shortest Ph Ph contacts, dihedral angles and twist angles in the determined crystal structures at 93, 298, and 373 K S7 Figure S4. 2 H NMR spectra of TPE-d 20 taken between 298 and 423 K S8 Figure S5. 2 H NMR spectra of 1c taken between 298 and 423 K S9 Figure S6. DFT-calculated PES for phenyl ring flipping in styrene and benzoic acid S10 Figure S7. DFT-calculated PES for phenyl ring flipping in 1 and H 4 TCPE fixed in MOF geometry S11 Figure S8. DFT-calculated PES for phenyl ring flipping in vinylbenzoic acid with orthogonal or coplanar ethylene and carboxylic acid groups S12 Figure S6. PXRD patterns of 1c and fully desolvated 1H S13 Figure S8. Geometry-optimized conformations of TPE at fixed C Ar C Ar C=C dihedral angles S14 S1

2 Table S3. Activation energies, C=C bond lengths, and selected angles for geometryoptimized conformations of TPE at fixed C Ar C Ar C=C dihedral angles S14 Table S4. Dihedral angles for geometry-optimized conformations of TPE at fixed C Ar C Ar C=C dihedral angles S14 Figure S9. DFT-calculated molecular conformations of truncated 1b model at fixed C Ar C Ar C=C dihedral angles S15 Table S5. Activation energies, C=C bond lengths, and selected angles for geometryoptimized molecular conformations of a truncated model of 1b at fixed C Ar C Ar C=C dihedral angles S15 Table S6. Dihedral angles for geometry-optimized molecular conformations of a truncated model of 1b at fixed C Ar C Ar C=C dihedral angles S15 Figure S10. DFT-calculated PES for phenyl ring flipping in terephthalic acid with coplanar ethylene and carboxylic acid groups S16 Table S7. Electron density at bond critical points for selected bonds along PES for ring flipping in truncated model of 1b S17 Scheme 1. Depiction of the proposed desolvation process that occurs during the conversion of 1b to 1c S18 Figure S11. Emission spectra of TPE (blue) and TPE-d 20 S19 Figure S12. Emission spectra of desolvated 1H and 1c S20 S2

3 Table S1. X-ray crystal structure refinement data a for TPE-d 20, 1a and 1b at various temperatures. TPE-d 20 (298 K) TPE-d 10 (373 K) 1a (100 K) 1b (373 K) formula C 26 D 20 C 26 D 20 Zn 2 C 30 D 16 O 8 (DEF) 2 2DEF Zn 2 C 30 D 16 O 8 (DEF) 2 FW T, K 298(1) 373(1) 100(1) 373(1) cryst. syst., space group Monoclinic P2 1 Monoclinic P2 1 Monoclinic C2/c Orthorhombic Ibam Z a, Å 9.837(8) 9.822(1) (2) (3) b, Å 9.489(8) 9.600(1) (1) (4) c, Å (9) (1) (2) (6) β, (1) (2) (2) 90 V, Å 3 956(1) 963.2(2) (7) 5488(2) d calc, g/cm µ, mm F(000) crystal size, mm theta range 1.99 to to to to index ranges 12 h h h h 6 11 k k 11 9 k k l k k k 18 refl. collected data/restr./param. 3902/ 1 / / 1 / / 310 / / 40 /142 GOF on F large peak/hole, 0.135/ / / / e/å 3 R 1 (wr 2 ), % [I>2sigma(I)] b 4.40 (12.24) 3.90 (11.59) 6.97 (22.07) 7.07 (27.64) a Mo-Kα (λ = Å) radiation b R 1 = Σ F o - F c / Σ F o, wr 2 = { Σ [w(f 2 o -F 2 c ) 2 ]/ Σ [w(f 2 o ) 2 ]} 1/2 S3

4 Figure S1. Thermogravimetric analysis plots for 1 (blue) and 1H (red). S4

5 Figure S2. Simulated (red) and experimental (black) PXRD patterns of 1c. S5

6 Figure S3. VT 1 H NMR spectra of TPE (left) and H 4 TCPE (right) in CD 2 Cl 2 and CD 3 OD, respectively. S6

7 Table S2. The shortest Ph Ph contacts, the dihedral angles and the ethylene twist angles in the determined crystal structures at 93, 298, and 373 K using the indices specified in the sample TPE structure shown above. T, K Ph Ph contacts, Å C=C, Å 3126, 4215, Ethylene twist, (3) 1.356(2) 10.2(1) 6.3(1) (6) 1.354(3) 10.6(2) 8.4(2) (5) 1.348(3) 11.1(2) 8.9(2) S7

8 Figure S4. 2 H NMR spectra of TPE-d 20 taken between 298 and 423 K. S8

9 Figure S5. 2 H NMR spectra of 1c taken between 298 and 423 K. S9

10 Energy (kj/mol) C Ar C Ar C=C Dihedral Angle (deg) Energy (kj/mol) C Ar C Ar C=O Dihedral Angle (deg) Figure S6. DFT-calculated PESs for phenyl ring flipping in styrene (top) and in benzoic acid (bottom). A line has been added as a visual guide. S10

11 60 50 Energy (kj/mol) C Ar C Ar C=C Dihedral Angle (deg) Figure S7. DFT-calculated PES for phenyl ring flipping in 1 ( ) and H 4 TCPE with O atoms fixed in MOF geometry ( ). Lines have been added as visual guides. S11

12 Energy (kj/mol) C Ar C Ar C=O Dihedral Angle (deg) Figure S8. DFT-calculated PES for phenyl ring flipping in vinylbenzoic acid with orthogonal ethylene and carboxylic acid groups ( ) and coplanar ethylene and carboxylic acid groups ( ). Lines have been added as a visual guide. S12

13 Figure S6. PXRD patterns of 1c (top) and fully desolvated 1H (bottom) after desolvation at 200 C. S13

14 Figure S8. Geometry-optimized conformations of TPE at 47.8, 0, and 90 dihedral angles (depicted by pink) as obtained by DFT calculations. Table S3. Activation energies, C=C bond lengths, and selected angles for geometryoptimized conformations of TPE at fixed C Ar C Ar C=C (47.8, 0, and 90) dihedral angles. Fixed dihedral angles, E, kj/mol C=C, Å 315, 426, 312, 421, 512, 621, 47.8 (min) (max) (local max) Table S4. Dihedral angles for geometry-optimized conformations of TPE at fixed C Ar C Ar C=C (47.8, 0, and 90) dihedral angles. Fixed dihedral angles, 3124, 5126, 3126, 5124, Ethylene twist, 47.8 (min) (max) (local max) S14

15 Figure S9. DFT-calculated molecular conformations of truncated 1b model at fixed C Ar C Ar C=C (125, 5, and 95) dihedral angles (depicted in pink). Table S5. Activation energies, C=C bond lengths, and selected angles for geometryoptimized molecular conformations of a truncated model of 1b at fixed C Ar C Ar C=C (125, 5, and 95) dihedral angles. Fixed dihedral angles, E, kj/mol C=C, Å 315, 426, 312, 421, 512, 621, 125 (min (max) (local max) Table S6. Dihedral angles for geometry-optimized molecular conformations of a truncated model of 1b at fixed C Ar C Ar C=C (125, 5, and 95) dihedral angles. Fixed dihedral angles, 3124, 5126, 3126, 5124, Ethylene twist, 125 (min) (max) (local max) S15

16 60 50 Energy (kj/mol) C Ar C Ar C=O Dihedral Angle (deg) Figure S10. DFT-calculated PES for phenyl ring flipping in terephthalic acid with coplanar ethylene and carboxylic acid groups ( ). A line has been added as a visual guide. S16

17 Table S7. Electron density (e Å 3 ) at bond critical points for selected bonds along PES for ring flipping in truncated model of 1b. C Ar C Ar C=C dihedral angle () ρ(c1 C3) ρ(c1 C5) ρ(c2 C4) ρ(c2 C6) ρ(c11 C15) ρ(c12 C16) ρ(c13 C17) ρ(c14 C18) ρ C C S17

18 Scheme S1. Depiction of the proposed desolvation process that occurs during the conversion of 1b to 1c. S18

19 Figure S11. Normalized emission spectra of TPE (blue) and TPE-d 20 (red) (λ ex = 335 nm). S19

20 Figure S12. Normalized emission spectra of desolvated 1H (blue) and 1c (red) (λ ex = 350 nm). S20