From Trigonal Bipyramidal to Platonic Solids: Self- Assembly and Self-Sorting Study of Terpyridine-Based 3D

Transcription

1 From Trigonal Bipyramidal to Platonic Solids: Self- Assembly and Self-Sorting Study of Terpyridine-Based 3D Architectures Ming Wang,, Chao Wang,, Xin-Qi Hao, *, Xiaohong Li, Tyler J Vaughn, Yan-Yan Zhang, # Yihua Yu, # Zhong-Yu Li, Mao-Ping Song, Hai-Bo Yang, and Xiaopeng Li*, Department of Chemistry and Biochemistry, Texas State University, San Marcos, TX 78666, United States College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou , China College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou , China # Shanghai Key Laboratory of Magnetic Resonance, Department of Physics, East China Normal University, Shanghai , China Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai , China X_L8@txstate.edu, xqhao@zzu.edu.cn Table of Contents 1. Synthetic route of the ligands and complexes S2 2. Experimental Section...S3-S4 3. Synthesis of the ligands and complexes.s5-s12 4. ESI mass spectra data of Complex A, Complex B and Complex C...S13-S17 5. Calibration of drift time scale......s18 6. Photophysical properties of ligands and complexes...s H NMR, 13 C NMR, 2D COSY NMR, HMBC NMR and HSQC NMR...S20-S30 8. References....S31 S1

2 1. Synthetic route of ligands and complexes Scheme S1. Synthetic route of ligands and complexes. S2

3 2. Experimental Section General Procedures. All reagents were purchased from Aldrich, Matrix Scientific, Alfa Aesar and used without further purification. Compound 4-((trimethylsilyl)ethynyl)benzaldehyde, 1 5- ((trimethylsilyl)ethynyl)thiophene-2-carbaldehyde, 2 3-((trimethylsilyl)ethynyl)benzaldehyde, 3 1- (4-tert-butylpyridin-2-yl)ethanone 4 and 1,3,5,-tri(4-iodophenyl)-adamantane 5 were synthesized according to the reported methods. Column chromatography was conducted using basic Al 2 O 3 (Brockman I, activity, 58 Å) or SiO 2 (VWR, um, 60Å) and the separated products were visualized by UV light. 1 H NMR and 13 C NMR spectra data were recorded on a Bruker Avance 400-MHz and 600-MHz NMR spectrometer in CDCl 3 and CD 3 CN with TMS standard. UV vis absorption (UV) spectra were recorded with a Varian Cary 100 UV/Vis Spectrometer. Photoluminescence (PL) spectra were obtained on a PerkinElmer LS50B Luminescence spectrometer. Electrospray ionization (ESI) mass spectra were recorded with a Waters Synapt G2 tandem mass spectrometer, using solutions of 0.01mg sample in 1 ml of CHCl 3 /CH 3 OH (1:3, v/v) for ligand or 0.5 mg in 1 ml of MeCN/MeOH (3:1, v/v) for complex. The TWIM MS experiments were performed under the following conditions: ESI capillary voltage, 3kV; sample cone voltage, 30 V; extraction cone voltage, 3.5 V; source temperature 100 ºC; desolvation temperature, 100 ºC; cone gas flow, 10 L/h; desolvation gas flow, 700 L/h (N 2 ); source gas control, 0 ml/min; trap gas control, 2 ml/min; Helium cell gas control, 100 ml/min; ion mobility (IM) cell gas control, 30 ml/min; sample flow rate, 5 μl/min; IM traveling wave height, 25 V; and IM traveling wave velocity, 1000 m/s. Q was set in rf-only mode to transmit all ions produced by ESI into the triwave region for the acquisition of TWIM MS data. S3

4 Collision cross section calibration. The calibration procedure of Scrivens et al 6 was used to convert the drift time scale of the TWIM MS experiments to a collision cross section (CCS) scale via the calibration curve was constructed by plotting the corrected CCSs of the molecular ions of myoglobin and cytochrome C (horse heart) 7 against the corrected drift times of the corresponding molecular ions measured in TWIM MS experiments at the same traveling wave velocity, traveling wave height, and ion mobility gas flow settings viz., 1000m/s, 25 V, and 30 ml/min, respectively. Due to the size difference, the calibration curve myoglobin was used to calculate the CCS of complex A, and the calibration curve of cytochrome C was used to calculate the CCS of complex B. Molecular modeling. Energy minimization of these complexes was conducted with Materials Studio version 6.0, using the Anneal and Geometry Optimization tasks in the Forcite module (Accelrys Software, Inc.). All counterions are omitted. An initially energy-minimized structure was subjected to 50 annealing cycles with initial and mid-cycle temperatures of 300 and 1500 K, respectively, twenty heating ramps per cycle, one thousand dynamics steps per ramp, and one dynamics step per femtosecond. A constant volume/constant energy (NVE) ensemble was used and the geometry was optimized after each cycle. Geometry optimization used a universal force field with atom-based summation and cubic spline truncation for both the electrostatic and van der Waals parameters. 50 energy-minimized structures were selected for the calculation of theoretical collision cross-sections using MOBCAL programs. S4

5 3. Synthesis of the ligands and complexes Compound 1. To a solution of NaOH powder (1.6 g, 40 mmol) in 25 ml EtOH, 4- ((trimethylsilyl)ethynyl)benzaldehyde (1.0 g, 5.0 mmol) and 4-tert-Butyl-2-acetylpyridine (2.0 g, 11.3 mmol) was added. After stirring at 25 ºC for 6 h, aqueous NH 3.H 2 O (20 ml) was added and the mixture was refluxed for 20 h. After cooling to room temperature, the precipitate was filtered and washed with cold ethanol to give 1 as white solid: 1.2 g (54%); 1 H NMR (400 MHz, CDCl 3 ): δ 8.82 (dd, J = 2.1, 0.8 Hz, 2H, tpy-h 3,3'' ), 8.74 (s, 2H, tpy-h 3',5' ), 8.66 (dd, J = 5.2, 0.7 Hz, 2H, tpy-h 6,6'' ), (m, 2H, Ph-H B ), (m, 2H, Ph-H A ), 7.39 (dd, J = 5.2, 2.0 Hz, 2H, tpy-h 5,5'' ), 3.20 (s, 1H), 1.47 (s, 18H). 13 C NMR (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , 83.36, 78.44, 34.96, ESI-HRMS (): Calcd. For [C 31 H 31 N 3 +H] + : Found: S5

6 Ligand LA. To a flask containing Pd(PPh 3 ) 2 Cl 2 (56 mg, 0.08 mmol), CuI (7.6 mg, 0.04 mmol) and 1,3,5,-tri(4-iodophenyl)-adamantane (4) (370 mg, 0.5 mmol) in 20 ml THF, 8 ml Et 3 N was added. After stirring at room temperature for 10 minutes, the solution of the compound 1 (756 mg, 1.7 mmol) in 10 ml THF was slowly added over 1 h. The mixture was heated at 40 ºC for 2 days. After removal of the volatile, the residue was purified by column chromatography on Al 2 O 3 with chloroform as eluent to afford LA in 66% yield as a yellow solid. 1 H NMR (400 MHz, CDCl 3 ): δ 8.83 (s, J = 2.0, 0.8 Hz, 6H, tpy-h 3,3'' ), 8.77 (s, 6H, tpy-h 3',5' ), 8.67 (d, J = 5.2, 0.7 Hz, 6H, tpy-h 6,6'' ), (m, 6H, Ph-H D ), (m, 6H, Ph-H C ), 7.59 (d, J = 8.6 Hz, 6H, Ph-H B ), 7.49 (d, J = 8.8 Hz, 6H, Ph-H A ), 7.39 (dd, J = 5.3, 2.0 Hz, 6H, tpy-h 5,5'' ), 2.62 (m, 1H), 2.17 (s, 6H), 2.07 (s, 6H), 1.48 (s, 54H). 13 C NMR (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , 90.87, 88.89, 47.70, 41.21, 38.48, 34.99, 30.54, ESI-HRMS (): Calcd. for [C 121 H 115 N 9 +2H] 2+ and [C 121 H 115 N 9 +3H] 3+ : and Found: and S6

7 =Zn 2+ Complex A [Zn 12 LA 8 ]: To a solution of ligand LA (6.5 mg, 3.8 μmol) in CHCl 3 (1 ml), a solution of Zn(NO 3 ) 2 6H 2 O (1.7 mg, 5.7 μmol) in MeOH (3 ml) was added; then the mixture was stirred at 50 ºC for 8 h. After cooling to room temperature, 200 mg NH 4 PF 6 was added to give a white precipitate, and used water to wash and obtained product (yield: 93%). 1 H NMR (400 MHz, CD 3 CN): δ 9.09 (s, 6H, tpy-h 3',5' ), 8.69 (s, 6H, tpy-h 3,3'' ), 8.33 (s, 6H, Ph-H D ), 7.95 (s, 6H, Ph-H C ), 7.72 (m, 18H, tpy-h 6,6'', Ph-H B, and Ph-H A ), 7.44 (s, 6H, tpy-h 5,5'' ), 1.41 (s, 54H). 13 C NMR (150MHz, CD 3 CN): δ , , , , , , , , , , , , 38.25, 35.15, ESI MS (): [M-9PF 6 ] 9+ (calcd :1635.8), [M-10PF 6 ] 10+ (calcd : ), [M-11PF 6 ] 11+ (calcd : ), [M-12PF 6 ] 12+ (calcd : ), [M-13PF 6 ] 13+ (calcd : ), [M-14PF 6 ] 14+ (calcd : ), [M-15PF 6 ] 15+ (calcd : ), [M- 16PF 6 ] 16+ (calcd : 969.2), [M-17PF 6 ] 17+ (calcd :903.6), [M-18PF 6 ] 18+ (calcd : 845.4), [M-19PF 6 ] 19+ (calcd : 793.2), [M-20PF 6 ] 20+ (calcd : 746.4), [M-21PF 6 ] 21+ (calcd : 703.9), [M-22PF 6 ] 22+ (calcd : 665.3), and [M-23PF 6 ] 23+ (calcd : 630.0). S7

8 Compound 2. To a solution of NaOH powder (1.6 g, 40 mmol) in 25 ml EtOH, 5- ((trimethylsilyl)ethynyl)thiophene-2-carbaldehyde (1.2 g, 5.8 mmol) and 4-tert-Butyl-2- acetylpyridine (2.4 g, 13.6 mmol) was added. After stirring at 25 ºC for 6 h, aqueous CH 3 COONH 4 (2.7 g, 34.6 mmol) was added into the bottle, the mixture was refluxed for 15 h. After cooling to room temperature, the precipitate was filtered and washed with cold ethanol to give 2 as yellow solid: 1.5 g (58%); 1 H NMR (400 MHz, CDCl 3 ): δ 8.77 (dd, J = 2.0, 0.7 Hz, 2H, tpy-h 3,3'' ), (m, 4H, tpy-h 3',5' and tpy-h 6,6'' ), 7.65 (d, J = 3.9 Hz, 1H, Ph-H B ), 7.39 (dd, J = 5.2, 2.0 Hz, 2H, tpy-h 5,5'' ), 7.34 (d, J = 4.1 Hz, 1H, Ph-H A ), 3.47 (s, 1H), 1.47 (s, 18H). 13 C NMR (100 MHz, CDCl 3 ): , , , , , , , , , , , , 82.75, 76.86, 35.06, ESI-HRMS (): Calcd. for [C 29 H 29 N 3 S+H] + : Found: S8

9 Ligand LB. To a flask containing a solution of Pd(PPh 3 ) 2 Cl 2 (56 mg, 0.08 mmol), CuI (7.6 mg, 0.04 mmol) and 4 (296 mg, 0.4 mmol) in 25 ml THF added 10 ml Et 3 N. After stirring at room temperature for 10 minutes, the solution of the compound 2 (586 mg, 1.3 mmol) in 15 ml THF was slowly added over 1 h. The mixture was heated to 40 ºC for 2 days. The solvent was evaporated under the reduced pressure. The residue was purified by column chromatography on Al 2 O 3 with chloroform as eluent to afford LB in 55% yield as a red solid. 1 H NMR (400 MHz, CDCl 3 ): 1 H NMR (400 MHz, CDCl 3 ) δ 8.78 (dd, J = 2.0, 0.8 Hz, 6H, tpy-h 3,3'' ), 8.69 (s, 6H, tpy- H 3',5' ), 8.67 (dd, J = 5.3, 0.7 Hz, 6H, tpy-h 6,6'' ), 7.72 (d, J = 3.7 Hz, 3H, Ph-H D ), 7.56 (d, J = 8.5 Hz, 6H, Ph-H B ), 7.50 (s, 6H, Ph-H A ), 7.40 (dd, J = 5.4, 1.9 Hz, 6H, tpy-h 5,5'' ), 7.34 (d, J = 3.9 Hz, 3H, Ph-H C ), 2.62 (m, 1H), 2.16 (s, 6H), 2.06 (s, 6H), 1.47 (s, 54H). 13 C NMR (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , 94.88, 82.39, 47.62, 41.18, 38.50, 35.00, 30.53, ESI-HRMS (): Calcd. for [C 115 H 109 N 9 S 3 +2H] 2+ and [C 115 H 109 N 9 S 3 +3H] 3+ : and Found: and =Zn 2+ Complex B [Zn 6 LB 4 ]: To a solution of ligand LB (5.3 mg, 3.1 μmol) in CHCl 3 (1 ml), a solution of Zn(NO 3 ) 2 6H 2 O (1.4 mg, 4.7 μmol) in MeOH (3 ml) was added; then the mixture S9

10 was stirred at 50 ºC for 8 h. After cooling to room temperature, 220 mg NH 4 PF 6 was added and observed red precipitate, and used water to wash and obtained product (yield: 91%). 1 H NMR (400 MHz, CD 3 CN): δ 8.91 (s, 6H, tpy-h 3',5' ), 8.64 (s, 6H, tpy-h 3,3'' ), 8.29 (s, 3H, Ph-H D ), 7.68 (m, 21H, tpy-h 6,6'', Ph-H A, Ph-H B and Ph-H C ), 7.43 (s, 6H, tpy-h 5,5'' ), 1.40 (s, 54H). 13 C NMR (150 MHz, CD 3 CN): δ , , , , , 141,59, , , , , , , , , , , 96.23, 81.04, 38.40, 35.60, ESI MS (): [M-7PF 6 ] 7+ (calcd : ), [M-8PF 6 ] 8+ (calcd : 978.1), [M-9PF 6 ] 9+ (calcd : 853.3), [M-10PF 6 ] 10+ (calcd : 753.5), [M-11PF 6 ] 11+ (calcd : 671.9), and [M-12PF 6 ] 12+ (calcd : 603.7). Compound 3. To a solution of NaOH powder (1.6 g, 40 mmol) in 25 ml EtOH, 3- ((trimethylsilyl)ethynyl)benzaldehyde (1.0 g, 5.0 mmol) and 4-tert-Butyl-2-acetylpyridine (2.0 g, 11.3 mmol) was added. After stirring at 25 ºC for 6 h, aqueous NH 3 H 2 O (20 ml) was added into the bottle, the mixture was refluxed for 20 h. After cooling to room temperature, the precipitate was filtered and washed with cold ethanol to give 3 as white solid: 1.1 g (50 %); 1 H NMR (400 MHz, CDCl 3 ): δ 8.83 (dd, J = 2.1, 0.7 Hz, 2H, tpy-h 3,3'' ), 8.73 (s, 2H, tpy-h 3',5' ), 8.67 (dd, J = 5.2, 0.7 Hz, 2H, tpy-h 6,6'' ), (m, 1H, Ph-H A ), 7.91 (ddd, J = 7.7, 1.9, 1.2 Hz, 1H, Ph-H B ), 7.59 (dt, J = 7.7, 1.4 Hz, 1H, Ph-H C ), 7.49 (td, J = 7.7, 0.6 Hz, 1H, Ph-H D ), 7.39 (dd, J = 5.2, 2.0 Hz, 2H, tpy-h 5,5'' ), 3.16 (s, 1H), 1.48 (s, 18H). 13 C NMR (100 MHz, CDCl 3 ): δ , , S10

11 155.97, , , , , , , , , , , , 83.29, 77.71, 34.98, ESI-HRMS (): Calcd. for [C 31 H 31 N 3 +H] + : Found: Ligand LC. To a flask containing a solution of Pd(Pph 3 ) 2 Cl 2 (56 mg, 0.08 mmol), CuI (7.6 mg, 0.04 mmol) and 4 (222 mg, 0.3 mmol) in 20 ml THF added 8 ml Et3N. After stirring at room temperature for 10 minutes, the solution of the compound 3 (490 mg, 1.1 mmol) in 10 ml THF was slowly added over 1 h. The mixture was heated to 40 ºC for 2 days. The solvent was evaporated under the reduced pressure. The residue was purified by column chromatography on Al 2 O 3 with chloroform as eluent to afford LC in 71% yield as a yellow solid. 1 H NMR (400 MHz, CDCl 3 ): δ 8.83 (dd, J = 2.1, 0.7 Hz, 6H, tpy-h 3,3'' ), 8.76 (s, 6H, tpy-h 3',5' ), 8.67 (dd, J = 5.2, 0.7 Hz, 6H, tpy-h 6,6'' ), (m, 3H, Ph-H C ), 7.89 (ddd, J = 7.8, 1.9, 1.1 Hz, 3H, Ph-H D ), (m, 9H, Ph-H E and Ph-H B ), (m, 9H, Ph-H F and Ph-H A ), 7.39 (dd, J = 5.2, 2.0 Hz, 6H, tpy-h 5,5'' ), 2.62 (s, 1H), 2.19 (s, 6H), 2.06 (m, 6H), 1.48 (s, 54H). 13 C NMR (100 MHz, CDCl 3 ): δ , , , , , , , , , , , , , , , , , , 90.05, 88.74, 47.57, 41.21, S11

12 38.39, 34.95, 30.54, ESI-HRMS (): Calcd. for [C 121 H 115 N 9 +2H] 2+ and [C 121 H 115 N 9 +3H] 3+ : and Found: and =Zn 2+ Complex C [Zn 3 LC 2 ]: To a solution of ligand LC (5.6 mg, 3.3 μmol) in CHCl 3 (1 ml), a solution of Zn(NO 3 ) 2 6H 2 O (1.5 mg, 5.0 μmol) in MeOH (3 ml) was added; then the mixture was stirred at 50 ºC for 8 h. After cooling to room temperature, 200 mg NH 4 PF 6 was added and observed white precipitate, and used water to wash and obtained product (yield: 92%). 1 H NMR (400 MHz, CD 3 CN): δ 9.08 (d, J = 10.1 Hz, 6H, tpy-h 3',5' ), 8.68 (d, J = 7.2 Hz, 6H, tpy-h 3,3'' ), 8.41 (d, J = 20.6 Hz, 3H, Ph-H C ), 8.24 (s, 3H, Ph-H D ), (m, 6H, Ph-H E and Ph-H F ), (m, 18H, tpy-h 6,6'', Ph-H B and Ph-H A ), 7.42 (s, 6H, tpy-h 5,5'' ), 1.37 (s, 54H). 13 C NMR (100 MHz, CD 3 CN): δ , , , , , , , , , , , , , , , , , 90.17, 88.14, 46.72, 40.35, 39.37, 38.43, 35.37, ESI MS (): [M-3PF 6 ] 3+ (calcd : ), [M- 4PF 6 ] 4+ (calcd : 969.2), [M-5PF 6 ] 5+ (calcd : 746.3), and [M-6PF 6 ] 6+ (calcd : 597.6). S12

13 4. ESI mass spectra data of Complex A, Complex B and Complex C (PF 6 as counterion) Complex A: S13

14 S14

15 Figure S1. Measured (bottom) and calculated (top) isotope patterns for the different charge states (9+ to 23+) observed from [Zn 12 LA 8 ](PF 6 as counterion). S15

16 Complex B: Figure S2. Measured (bottom) and calculated (top) isotope patterns for the different charge states (7+ to 12+) observed from [Zn 6 LB 4 ](PF 6 as counterion). S16

17 Complex C: Figure S3. Measured (bottom) and calculated (top) isotope patterns for the different charge states (3+ to 6+) observed from [Zn 3 LC 2 ](PF6 as counterion). S17

18 Corrected Collision Cross-Section Corrected Collision Cross-Section 5. Calibration of drift time scale Figure S4. Plot of corrected drift times (arrival times) against corrected published cross sections for the multiply charged ions arising from myoglobin and cytochrome C (horse heart). Drift times were measured at a traveling wave velocity of 1000 m/s and a traveling wave height of 25 V. This calibration plot was utilized to obtain the experimental collision cross sections (CCSs) listed in Table y=114.23x R 2 = Corrected Drift Time Figure S4a. The calibration curve was constructed by plotting the corrected CCSs of the molecular ions of myoglobin for complex A y=132.99x R 2 = Corrected Drift Time Figure S4b. The calibration curve was constructed by plotting the corrected CCSs of the molecular ions of cytochrome C for complex B. S18

19 Normalized fluorescence Normalized absorbance 6. Photophysical properties of ligands and complexes a A B C LA LB LC Wavelength (nm) b A B C LA LB LC Wavelength (nm) Figure S5. The UV (5a) and PL (5b) spectra of ligands and complexes. S19

20 7. 1 H NMR, 13 C NMR, 2D COSY NMR, HMBC NMR and HSQC NMR. Figure S6. 1 H NMR (400 MHz) spectrum of complex A. Figure S7. 13 C NMR (600 MHz) spectrum of complex A. S20

21 Figure S8. 2D COSY (400 MHz) spectrum of complex A. Figure S9. HMBC NMR (600 MHz) spectrum of complex A. S21

22 Figure S10. HSQC NMR (600 MHz) spectrum of complex A. Figure S11. 1 H NMR (400 MHz) spectrum of complex B. S22

23 Figure S C NMR (600 MHz) spectrum of complex B. Figure S13. 2D COSY NMR (400 MHz) spectrum of complex B. S23

24 Figure S14. HMBC NMR (600 MHz) spectrum of complex B. Figure S15. HSQC NMR (600 MHz) spectrum of complex B. S24

25 Figure H NMR (400 MHz) spectrum of complex C. Figure C NMR (400 MHz) spectrum of complex C. S25

26 Figure S18. 2D COSY NMR (400 MHz) spectrum of complex C. Figure S19. 1 H NMR (400 MHz) spectrum of ligand LA. S26

27 Figure S C NMR (400 MHz) spectrum of ligand LA Figure S21. 2D COSY NMR (400 MHz) spectrum of ligand LA. S27

28 Figure S22. 1 H NMR (400 MHz) spectrum of ligand LB. Figure S C NMR (400 MHz) spectrum of ligand LB. S28

29 Figure S24. 2D COSY NMR (400 MHz) spectrum of ligand LB. Figure H NMR (400 MHz) spectrum of ligand LC. S29

30 Figure S C NMR (400 MHz) spectrum of ligand LC. Figure S27. 2D COSY NMR (400 MHz) spectrum of ligand LC. S30

31 7. References (1) (a) Y. Chen, Y. Wu, P. Henklein, X. Li, K. P. Hofmann, K. Nakanishi, O. P. Ernst, Chem. Eur. J. 2010, 16, 7389; (b) X. Wang, V. Ervithayasuporn, Y. Zhang, Y. Kawakami, Chem. Commun. 2011, 47, (2) J.-L. Fillaut, J. Perruchon, P. Blanchard, J. Roncali, S. Golhen, M. Allain, A. Migalsaka-Zalas, I. V. Kityk, B. Sahraoui, Organometallics 2005, 24, 687. (3) (a) M. Tanasova, B. Borhan, Eur. J. Org. Chem. 2012, 3261; (b) C. Frixa, M. F. Mahon, A. S. Thompson, M. D. Threadgill, Org. Biomol. Chem. 2003, 1, 306. (4) S. Perera, X. Li, M. Guo, C. Wesdemiotis, C. N. Moorefield, G. R. Newkome, Chem. Commun. 2011, 47, (5) D. N. Chin, D. M. Gordon, G. M. Whitesides, J. Am. Chem. Soc. 1994, 116, (6) K. Thalassinos, M. Grabenauer, S. E. Slade, G. R. Hilton, M. T. Bowers, J. H. Scrivens, Anal. Chem. 2009, 81, (7) F. A. Fernandez-Lima, R. C. Blase, D. H. Russell, Int. J. Mass spectrum. 2010, 298, S31