A Facile Approach Towards Multicomponent Supramolecular Structures: Selective Self- Assembly via Charge Separation Yao-Rong Zheng,* Zhigang Zhao, Ming Wang, Koushik Ghosh, J. Bryant Pollock, Timothy R. Cook, and Peter J. Stang* Department of Chemistry, University of Utah, 315 South 1400 East, RM, 2020, Salt Lake City, Utah, 84112 E-mail: stang@chem.utah.edu, zheng@chem.utah.edu 1. 1 H NMR Spectra of Multicomponent Supramolecular Rectangle 4, Trigonal Prism 7, and Tetragonal Prisms 8.....S2 2. ESI Mass Spectra of Multicomponent Supramolecular Trigonal Prism 7 and Tetragonal Prism 8b.... S4 3. 1 H NMR spectra and ESI Mass Spectra of Homoleptic Self-assembly 9, 10, and 11, and Neutral Triangle 12...S5 4. Experimental Details of Supramolecular Transformations... S9 5. 31 P {1 H} NMR Spectrum and ESI-MS of Multicomponent Porphyrin Cage 14.....S12 6. Experimental Details for the Pulsed Field Gradient Spin Echo (PGSE) NMR Measurements.....S13 7. Details for the Computational Simulations Using Maestro TM and Macromodel TM..S15 S1
Figure S1. Partial 1 H NMR (Acetone-d 6, 300MHz) spectrum of multicomponent supramolecular rectangle 4. Figure S2. Partial 1 H NMR (Acetone-d 6, 300MHz) spectrum of multicomponent supramolecular trigonal prism 7. S2
Figure S3. Partial 1 H NMR (Acetone-d 6, 300MHz) spectrum of multicomponent supramolecular tetragonal prism 8a. Figure S4. Partial 1 H NMR (CD 3 NO 2, 300MHz) spectrum of multicomponent supramolecular tetragonal prism 8b. S3
Figure S5. ESI mass spectrum of multicomponent supramolecular trigonal prism 7. Figure S6. ESI mass spectrum of multicomponent supramolecular tetragonal prism 8b. S4
Figure S7. Partial 1 H NMR (Acetone-d 6, 300MHz) spectrum of homoleptic self-assembly 9. Figure S8. Calculated (blue, top) and Experimental (red, bottom) ESI mass spectrum of homoleptic self-assembly 9. S5
Figure S9. Partial 1 H NMR (Acetone-d 6, 300MHz) spectrum of homoleptic self-assembly 10. Figure S10. Calculated (blue, top) and Experimental (red, bottom) ESI mass spectrum of homoleptic self-assembly 10. S6
Figure S11. Partial 1 H NMR (CD 3 NO 2 /CD 2 Cl 2 = 1:3, 300MHz) spectrum of homoleptic self-assembly 11. Figure S12. Calculated (blue, top) and Experimental (red, bottom) ESI mass spectrum of homoleptic self-assembly 11. Figure S13. Different views of the computational model (MMFF) of homoleptic self-assembly 11 and its estimated size. S7
Figure S14. 1 H NMR (Acetone-d 6, 300MHz) spectrum of neutral triangle 12. Figure S15. Calculated (blue, top) and Experimental (red, bottom) ESI mass spectrum of neutral triangle 12. S8
Procedure of Supramolecular Transformations Homoleptic self-assembly 9, 10, and 11 was obtained in Acetone-d 6 or CD 3 NO 2 /CD 2 Cl 2 mixed solvent, and neutral triangle 12 was formed in Acetone-d 6. Homoleptic self-assembly was then slowly added into the solution of neutral triangle in a 3:4 (9:12), 1:2 (10:12), and 1:2 (11:12) ratio, respectively. After 5 h of heating at 75 o C, clear solutions were obtained and concentrated by N 2 flow. Multinuclear ( 31 P and 1 H) NMR spectroscopy was used to characterize the solutions. Figure S16. Partial 1 H NMR spectra of multicomponent supramolecular rectangle 4 (a), trigonal prism 7 (b), and tetragonal prism 8b (c) obtained via supramolecular transformations. S9
Procedure of the Gradual Supramolecular Transformation of Homoleptic Square 9 into Multicomponent Rectangle 4 Homoleptic self-assembly 9 and neutral triangle 12 were obtained in Acetone-d 6, respectively. 9 and 12 were then mixed in a 3:0.4 (10% of 12), 3:1 (25% of 12), 3:2 (50% of 12), and 3:4 (100% of 12) ratio, respectively. After 5 h of heating at 75 o C, a clear solution was obtained and concentrated by N 2 flow. Multinuclear ( 31 P and 1 H) NMR spectroscopy was used to characterize the solutions. Figure S17. Partial 1 H NMR spectra for mixtures of square 9 upon addition of 0% (a), 10% (b), 25% (c), 50% (d), and 100% (e) of neutral triangle 12. S10
Figure S18. Calculated (blue, top) and Experimental (red, bottom) ESI mass spectrum of the intermediate formed during the gradual transformation (the intermediate is formed by [3 + 2 + 1] assembly of 90 acceptor 1, pyridyl donor 3, and carboxylate ligand 2). S11
Figure S19. 31 P{ 1 H} NMR (D 2 O/Acetone-d 6 = 1:1, 300MHz) spectrum of multicomponent porphyrin cage 14. Figure S20. Calculated (blue, top) and Experimental (red, bottom) ESI mass spectrum of multicomponent porphyrin cage 14. S12
Experimental Details for the Pulsed Field Gradient Spin Echo (PGSE) NMR Measurement Pulsed gradient spin-echo (PGSE) NMR diffusion measurements were done by pulse-sequence developed by Stejskal and Tanner. 1 Temp: 298K Instrument: Inova 500 MHz Stokes-Einstein Equation: The molecular size is obtained from the diffusion coefficient via the Stokes-Einstein equation where k B is the Boltzmann constant, T is the absolute temperature and r H is the hydrodynamic radius of the species under investigation. Gradient Calibration: The gradient strengths need to be carefully calibrated to obtain accurate D values to fit equation (1). Gradient strengths were calibrated using the width (in Hz) of a sample of known length along the NMR-tube (Z) axis, back-calculation of the coil constant from a diffusion experiment on D 2 O using D = 1.9 10-5 cm 2 /s for D 2 O at 298K 2 was used to calculate the gradient strengths of both the probes. S13
Issue of Viscosity: The effect of variable viscosity in different batch of same solvents was examined using the D values observed for the residual protons of the solvent resonance. Pulse sequence: Stejskal-Tanner pulse sequence Diffusion coefficients (D) D (7) : 5.88 ( ± 0.07) X 10-6 cm 2 /s in Acetone-d 6 D (8a) : 6.14 ( ± 0.04) X 10-6 cm 2 /s in Acetone-d 6 D (8b) : 3.34 ( ± 0.03) X 10-6 cm 2 /s in CD 3 NO 2 D (11) : 2.10 ( ± 0.01) X 10-6 cm 2 /s in CD 3 NO 2 Reference: 1. Stejskal, E. O.; Tanner, J. E. J. Chem. Phys. 1965, 42, 288. 2. Longsworth, L. G. J. Phys. Chem. 1960, 64, 1914. S14
Details for the Computational Simulations Using Maestro TM Macromodel TM and The license for Maestro and Macromodel was bought from Schrödinger TM. All computational models were initially built using Maestro, and then minimized by Macromodel. Molecular dynamics simulations using a MMFF or MM2* force field, 300K, in the gas phase (the computational simulation for the encapsulated complex 14 TP is in water phase) was used to equilibrate each supramolecule, and the output of the simulation was then minimized to full convergence. Parameters Used for Dynamics Simulations: Force Field: MMFF (MM2* for 8b and 14 TP) Solvent: None (Water for 14 TP) Electrostatic Treatment: Constant Dielectric Dielectric Constant: 1.0 Charge from: Force Field Cutoff: Normal Minimization Method: PRCG Maximum Iterations: 50000 Convergence Threshold: 0.0500 Dynamics: Stochastic Dynamics SHAKE: Nothing Simulation Temperature (K): 300.0 Time Step (fs): 1.500 Equilibration Time (ps): 1000.0 Simulation Time (ps): 10000.0 S15
Computational Models and their Corresponding Energies: Homoleptic Coordination Heteroleptic Coordination S16