SUPPLEMENTARY INFORMATION

Size: px
Start display at page:

Download "SUPPLEMENTARY INFORMATION"

Transcription

1 SUPPLEMENTARY INFORMATION Supplementary Information for Ion-triggered spring-like motion of a double helicate accompanied by anisotropic twisting Kazuhiro Miwa, Yoshio Furusho* and Eiji Yashima* Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya , Japan. * furusho@apchem.nagoya-u.ac.jp; yashima@apchem.nagoya-u.ac.jp nature chemistry 1

2 supplementary information 1. Instruments Melting points were measured on a Yanaco MP-500 micro melting point apparatus and were uncorrected. NMR spectra were measured on a Varian UNITY INOVA 500AS spectrometer operating at 500 MHz for 1 H and at 125 MHz for 13 C. Absorption and CD spectra were measured using a JASCO V-570 spectrophotometer and a JASCO J-820 spectropolarimeter, respectively. Stopped-flow CD spectroscopy was measured on a JASCO J-820 spectropolarimeter with an SFS-492 stopped-flow attachment. Electrospray ionization (ESI) mass spectra were recorded on a JEOL JMS-T100CS mass spectrometer. The single-crystal X-ray data for the helicates, DH2 BNaB BMAmm + and DH2 BB 2 (BMAmm + ) 2, were collected on a Bruker Smart Apex CCD-based X-ray diffractometer with Mo-Kα radiation (λ = Å). 2. Materials All starting materials were purchased from commercial suppliers and were used without further purification unless otherwise noted. The boronic acid, 3 1, and the dibromide, 4 2, were prepared according to the literature. 3. Synthesis and Characterization of the Tetraphenol (2) The ligand, H 4 L2 (2), was synthesized by the Suzuki cross-coupling of 3 1 and 4, 2 followed by demethylation with BBr 3, as shown in Scheme S1. 2 Bu t MeO OMe B(OH) 2 Bu t + Br Br Pd(PPh 3 ) 4 K 2 CO 3 aq toluene, 100 C (77% yield) OMe Bu t OMe Bu t OMe Bu t OMe Bu t OH OH OH OH i) BBr 3 ii) H 2 O (60% yield) Bu t Bu t Bu t Bu t 2: H 4 L2 Scheme S1. Synthesis of tetraphenol 2. 2 nature chemistry

3 supplementary information 5: A mixture of 3 (800 mg, 2.16 mmol), 4 (270 mg, mmol), and Pd(PPh 3 ) 4 (130 mg, mmol) in toluene (8.0 ml) and 2 M aq. K 2 CO 3 (8.0 ml) was stirred at 100 C for 18 h under an Ar atmosphere. The mixture was extracted with EtOAc (80 ml). The organic layer was washed with H 2 O (40 ml) and brine (40 ml), dried over anhydrous Na 2 SO 4, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (SiO 2 (120 g), n-hexane/etoac = 10/0 to 8/2) to give 5 as a white solid in 77% yield. This compound was used in the next step without further purification. 1 H NMR (500 MHz, CDCl 3, 25 C, 5.3 mm) δ 7.89 (m, 2H, ArH), (m, 4H, ArH), 7.50 (dd, J = 7.7 Hz, 7.7 Hz, 2H, ArH), (m, 4H, ArH), (m, 4H, ArH), 6.94 (d, J = 8.6 Hz, 2H, ArH), 3.79 (s, 6H, OCH 3 ), 3.25 (s, 6H, OCH 3 ), 1.36 (s, 18H, t-bu), 1.33 (s, 18H, t-bu). H 4 L2 (2): To a solution of 5 (1.08 g, 1.34 mmol) in CH 2 Cl 2 (42 ml) was added a 1.0 M CH 2 Cl 2 solution of BBr 3 (26.8 ml, 26.8 mmol) at 80 C under an Ar atmosphere. After being warmed to room temperature, the mixture was stirred for 17 h. Then, H 2 O (60 ml) was added to the mixture at 5 C, which was stirred for 1 h at room temperature. The mixture was then evaporated to remove CH 2 Cl 2 and the resultant aqueous solution was extracted with EtOAc (3 80 ml). The combined organic layer was washed with 1 M HCl (80 ml), H 2 O (80 ml), and brine (80 ml), dried over anhydrous MgSO 4, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (SiO 2 (120 g), n-hexane/etoac = 10/0 to 7/3) to give H 4 L2 (2) as a white solid in 60% yield. M.p. = C; 1 H NMR (500 MHz, CDCl 3, 25 C, 5.7 mm) δ 7.84 (m, 2H, ArH), 7.67 (dd, J = 6.9 Hz, 1.9 Hz, 2H, ArH), (m, 4H, ArH), 7.40 (d, J = 2.5 Hz, 2H, ArH), 7.36 (dd, J = 8.5 Hz, 2.5 Hz, 2H, ArH), (m, 4H, ArH), 7.00 (d, J = 8.5 Hz, 2H, ArH), 5.69 (s, 2H, OH), 5.59 (s, 2H, OH), 1.36 (s, 18H, t-bu), 1.34 (s, 18H, t-bu); ESI-MS (CH 3 CN, negative): m/z = 745 [M H] ; Anal. Calcd for C 52 H 58 O 4 : C, 83.61; H, Found: C, 83.62; H, NMR Data of the Helicates (±)-DH2 BNaB Na + : 1 H NMR (500 MHz, acetone-d 6, 25 C, 0.9 mm) δ 7.55 (dd, J = 7.7 Hz, 7.7 Hz, 4H, ArH), (m, 8H, ArH), 7.30 (d, J = 2.7 Hz, 4H, ArH), 6.97 (br t, 4H, ArH), 6.92 (d, J = 2.7 Hz, 4H, ArH), 6.78 (d, J = 2.5 Hz, 4H, ArH), 6.34 (dd, J = 8.3 Hz, 2.5 Hz, 4H, ArH), 5.49 (d, J = 8.3 Hz, 4H, ArH), 1.35 (s, 36H, t-bu), 0.93 (s, 36H, t-bu); 13 C nature chemistry 3

4 supplementary information NMR (125 MHz, acetone-d 6, 25 C, 2.8 mm) δ 153.3, 151.2, 143.0, 142.3, 141.4, 141.3, 134.1, 134.0, 130.6, 130.0, 129.2, 128.8, 128.0, 126.8, 125.8, 125.5, 124.9, 120.5, 34.6, 34.1, 32.0, (±)-DH2 BNaB BMAmm + : H NMR (500 MHz, CD 3 CN, 25 C) δ (m, 17H, ArH), 7.27 (d, J = 2.7 Hz, 4H, ArH), 6.90 (d, J = 2.7 Hz, 4H, ArH), 6.74 (d, J = 2.5 Hz, 4H, ArH), 6.41 (br t, 4H, ArH), 6.29 (dd, J = 8.3 Hz, 2.5 Hz, 4H, ArH), 5.32 (d, J = 8.2 Hz, 4H, ArH), 4.36 (s, 2H, CH 2 N), 2.98 (s, 12H, NCH 3 ), 1.30 (s, 36H, t-bu), 0.84 (s, 36H, t-bu). (+)-DH2 BNaB ( )-DMEph + : 1 H NMR (500 MHz, CD 2 Cl 2, 25 C, 0.8 mm) δ (m, 9H, ArH), (m, 2H, ArH), 7.22 (d, J = 2.6 Hz, 4H, ArH), (m, 4H, ArH), 6.94 (d, J = 2.5 Hz, 4H, ArH), 6.87 (d, J = 7.3 Hz, 2H), 6.80 (d, J = 2.6 Hz, 4H, ArH), 6.29 (br t, 4H, ArH), 6.27 (dd, J = 8.3 Hz, 2.6 Hz, 4H, ArH), 5.56 (d, J = 4.8 Hz, 1H, CHOH), (m, 4H, ArH), 4.71 (d, J = 4.8 Hz, 1H, OH), (m, 2H, CH 2 N), (m, 1H, CHCH 3 ), 2.59 (s, 3H, CH 3 N), 2.47 (s, 3H, CH 3 N), 1.32 (s, 36H, t-bu), (m, 26H, CHCH 3, (CH 2 ) 10 CH 3 ), 0.83 (s, 36H, t-bu). (+)-DH2 BNaB TBAmm + (93% e.e.): 1 H NMR (500 MHz, CD 2 Cl 2, 25 C, 0.6 mm) δ (m, 4H, ArH), (m, 8H, ArH), 7.27 (d, J = 2.6 Hz, 4H, ArH), 6.94 (d, J = 2.7 Hz, 4H, ArH), 6.81 (d, J = 2.6 Hz, 4H, ArH), 6.42 (br t, 4H, ArH), 6.30 (dd, J = 8.3 Hz, 2.6 Hz, 4H, ArH), 5.40 (d, J = 8.3 Hz, 4H, ArH), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), 1.31 (s, 36H, t-bu), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), 0.85 (s, 36H, t-bu), 0.77 (t, J = 7.3 Hz, 12H, NCH 2 CH 2 CH 2 CH 3 ). 1 H NMR (500 MHz, CD 3 CN, 25 C, 0.3 mm) δ (m, 12H, ArH), 7.27 (d, J = 2.6 Hz, 4H, ArH), 6.90 (d, J = 2.6 Hz, 4H, ArH), 6.73 (d, J = 2.5 Hz, 4H, ArH), 6.41 (br t, 4H, ArH), 6.28 (dd, J = 8.3 Hz, 2.5 Hz, 4H, ArH), 5.32 (d, J =8.3 Hz, 4H, ArH), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), 1.31 (s, 36H, t-bu), 0.96 (t, J = 7.3 Hz 12H, NCH 2 CH 2 CH 2 CH 3 ), 0.84 (s, 36H, t-bu). (+)-DH2 BB 2 TBAmm + Na + 221: 1 H NMR (500 MHz, CD 3 CN, 25 C, 0.3 mm) δ 7.53 (d, J = 8.0 Hz, 4H, ArH), 7.43 (d, J = 2.7 Hz, 4H, ArH), 7.41 (d, J = 2.5 Hz, 4H, ArH), 7.17 (d, J = 2.5 Hz, 4H, ArH), 7.16 (dd, J = 8.2 Hz, 2.1 Hz, 4H, ArH), (m, 8H, ArH), 6.68 (t, J = 7.7 Hz, 4H, ArH), 6.55 (d, J = 8.4 Hz, 4H, ArH), (m, 20H, 221), (m, 4 nature chemistry

5 supplementary information 8H, NCH 2 CH 2 CH 2 CH 3 ), (m, 12H, 221), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), 1.45 (s, 36H, t-bu), 1.36 (s, 36H, t-bu), (m, 8H, NCH 2 CH 2 CH 2 CH 3 ), 0.96 (t, J = 7.3 Hz, 12H, NCH 2 CH 2 CH 2 CH 3 ). nature chemistry 5

6 supplementary information X-ray Crystallographic Data of (±)-DH2 BNaB BMAmm + X-ray diffraction data for (±)-DH2 BNaB BMAmm + were collected on a Bruker Smart Apex CCD-based X-ray diffractometer with Mo-Kα radiation (λ = Å) at 153 K. Single crystals of (±)-DH2 BNaB BMAmm + [C 126 H 142 B 2 N 7 NaO 8, MW = ] suitable for X-ray analysis were grown by slow evaporation of an CH 3 CN solution, and a single colorless crystal with dimensions mm 3 was selected for intensity measurements. The unit cell was monoclinic with the space group P2 1 /c. Lattice constants with Z = 4, ρ calcd = g cm 3, μ(mo Kα) = mm 1, F(000) = 4128, 2θ max = were a = (2) Å, b = (4), c = (4) Å, β = (3), and V = 11,151(3) Å 3. A total of 81,641 reflections was collected, of which 27,780 reflections were independent (R int = ). The structure was refined to final R 1 = for 19,203 data [I>2σ(I)] with 1,677 parameters and wr 2 = for all data, GOF = 1.044, and residual electron density max/min = 1.183/ e Å 3. The ORTEP drawing is shown in Figure S1, and crystal data and structure refinement are listed in Table S1. Data collection, indexing, and initial cell refinements were carried out using the program SMART 3. Frame integration and final cell refinements were performed using SAINT software 4. A multiple absorption correction for each data set was applied using the program SADABS 5. The structure was solved by direct methods and Fourier techniques using the program SIR-97 6 and refined by full-matrix least squares methods on F 2 using SHELXL-97 7 incorporated in SHELXTL-PC 8. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were calculated geometrically and refined using the riding models. Some t-butyl groups showed high Ueq(max)/Ueq(min) ratios for C atoms. We tried to resolve these problems by assigning alternative positions with partial occupancies for the t-butyl groups, but some of the atoms continue to have the high Ueq(max)/Ueq(min) ratios, which are indicative of the dynamic nature of the disorder in these t-butyl groups. 6 nature chemistry

7 supplementary information Figure S1. ORTEP drawing of the crystal structure of (±)-DH2 BNaB BMAmm + with thermal ellipsoids at 50% probability. nature chemistry 7

8 supplementary information Table S1. Crystal data and structure refinement for (±)-DH2 BNaB BMAmm + Empirical formula (C 114 H 124 B 2 NNaO 8 ) (C 2 H 3 N) 6 Formula weight Temperature 153 K Wavelength Å Crystal system Monoclinic Space group P2 1 /c Unit cell dimensions a = (2) Å α = 90. b = (4) Å β = (3). c = (4) Å γ = 90. Volume 11,151(3) Å 3 Z 4 Density (calculated) g cm 3 Absorption coefficient mm 1 F(000) 4,128 Crystal size mm 3 Theta range for data collection 1.08 to Index ranges 20 h 20, 36 k 28, 35 l 35 Reflections collected 81,641 Independent reflections 27,780 [R int = ] Completeness to theta 99.7% Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 27,780 / 0 / 1,677 Goodness-of-fit on F Final R indices [I>2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e Å 3 CCDC reference number CCDC nature chemistry

9 supplementary information ESI-MS Spectra of DH2 BNaB Na + Figure S2. Negative mode ESI mass spectra of DH2 BNaB Na + in CH 3 CN. nature chemistry 9

10 supplementary information gcosy Spectrum of DH2 BNaB Na + Figure S MHz gcosy spectrum of DH2 BNaB Na + (acetone-d 6, 25 C, 3.7 mm). 10 nature chemistry

11 supplementary information Figure S4. Partial 500 MHz gcosy spectrum of DH2 BNaB Na + (acetone-d 6, 25 C, 3.7 mm). nature chemistry 11

12 supplementary information NOESY Spectrum of DH2 BNaB Na + Figure S MHz NOESY spectrum of DH2 BNaB Na + (acetone-d 6, 25 C, 3.7 mm, mixing time = 0.5 s). 12 nature chemistry

13 supplementary information Figure S6. Partial 500 MHz NOESY spectrum of DH2 BNaB Na + (acetone-d 6, 25 C, 3.7 mm, mixing time = 0.5 s). nature chemistry 13

14 supplementary information Figure S7. Partial 500 MHz NOESY spectrum of DH2 BNaB Na + (acetone-d 6, 25 C, 3.7 mm, mixing time = 0.5 s). 14 nature chemistry

15 supplementary information CD and UV/Vis Spectra of (+)-DH2 BNaB DMEph +, ( )-DH2 BNaB DMEph +, and (+)-DH2 BNaB TBAmm + Figure S8. CD and UV/Vis spectra (CH 3 CN, 25 C) of (+)-DH2 BNaB DMEph + (93% d.e.) (blue), ( )-DH2 BNaB DMEph + (29% d.e.) (red), and (+)-DH2 BNaB TBAmm + (93% e.e.) (dashed light blue). nature chemistry 15

16 supplementary information Determination of the Diastereomeric Excess by NMR spectroscopy Figure S MHz 1 H NMR spectra (CD 2 Cl 2, 25 C) of (a) the filtrate (( )-DH2 BNaB DMEph + (29% d.e.)) + ( )-DMEph + Br (ca. 9 eq) and (b) the precipitate ((+)-DH2 BNaB DMEph + (93% d.e.)). 16 nature chemistry

17 supplementary information Figure S10. Partial 500 MHz 1 H NMR spectra (CD 2 Cl 2, 25 C) of (a) the filtrate (( )-DH2 BNaB DMEph + (29% d.e.)) + ( )-DMEph + Br (ca. 9 eq) and (b) the precipitate ((+)-DH2 BNaB DMEph + (93% d.e.)). The d.e. of the filtrate was determined based on its relative CD intensity at 313 nm to that of the precipitate. nature chemistry 17

18 supplementary information Replacement of the Chiral Cation of (+)-DH2 BNaB DMEph + with an Achiral Cation Figure S MHz 1 H NMR spectra (CD 2 Cl 2, 25 C) of (a) (+)-DH2 BNaB DMEph + (93% d.e.) and (b) the corresponding enantiomeric (+)-DH2 BNaB TBAmm + (93% e.e.) after replacement of ( )-DMEph + with achiral TBAmm nature chemistry

19 supplementary information Figure S12. Partial 500 MHz 1 H NMR spectra (CD 2 Cl 2, 25 C) of (a) (+)-DH2 BNaB DMEph + (93% d.e.) and (b) the corresponding enantiomeric (+)-DH2 BNaB TBAmm + (93% e.e.) after replacement of ( )-DMEph + with achiral TBAmm +. nature chemistry 19

20 supplementary information X-ray Crystallographic Data of DH2 BB 2 (BMAmm + ) 2 X-ray diffraction data for (±)-DH2 BB 2 (BMAmm + ) 2 were collected on a Bruker Smart Apex CCD-based X-ray diffractometer with Mo-Kα radiation (λ = Å) at 153 K. Single crystals of (±)-DH2 BB 2 (BMAmm + ) 2 [(C 124 H 140 B 2 N 2 O 8 ) (C 2 N), MW = ] suitable for X-ray analysis were grown by slow evaporation of an CH 3 CN solution, and a single colorless crystal with dimensions mm 3 was selected for intensity measurements. The unit cell was orthorhombic with the space group Pcc2. Lattice constants with Z = 4, ρ calcd = g cm 3, μ(mo Kα) = mm 1, F(000) = 3,964, 2θ max = were a = (3) Å, b = (4), c = (6) Å,, and V = 12,118(4) Å 3. A total of 85,762 reflections was collected, of which 27,659 reflections were independent (R int = ). The structure was refined to final R 1 = for 16,428 data [I>2σ(I)] with 1,280 parameters and wr 2 = for all data, GOF = 1.057, and residual electron density max/min = 0.908/ e Å 3. The ORTEP drawing is shown in Figure S13, and crystal data and structure refinement are listed in Table S2. Data collection, indexing, and initial cell refinements were carried out using the program SMART 3. Frame integration and final cell refinements were performed using SAINT software 4. A multiple absorption correction for each data set was applied using the program SADABS 5. The structure was solved by direct methods and Fourier techniques using the program SIR-97 6 and refined by full-matrix least squares methods on F 2 using SHELXL-97 7 incorporated in SHELXTL-PC 8. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were calculated geometrically and refined using the riding models. Some t-butyl groups showed high Ueq(max)/Ueq(min) and ADP ratios for C atoms. We tried to resolve these problems by assigning alternative positions with partial occupancies for the t-butyl groups, but some of the atoms continue to have the high Ueq(max)/Ueq(min) and ADP ratios, which are indicative of the dynamic nature of the disorder in these t-butyl groups. In addition, the benzyl groups of the ammonium cation showed the disordered feature. We have tried to resolve it by assigning alternative positions for the C atoms, which did not work out, leaving a large solvent accessible void in the structure. This indicates the dynamic nature of the disorder in the ammonium cation moiety. 20 nature chemistry

21 supplementary information Figure S13. ORTEP drawing of the crystal structure of (±)-DH2 BB 2 (BMAmm + ) 2 with thermal ellipsoids at 50% probability. nature chemistry 21

22 supplementary information Table S2. Crystal data and structure refinement for (±)-DH2 BB 2 (BMAmm + ) 2 Empirical formula (C 124 H 140 B 2 N 2 O 8 ) (C 2 N) Formula weight Temperature 153 K Wavelength Å Crystal system orthorhombic Space group Pcc2 Unit cell dimensions a = (3) Å α = 90. b = (4) Å β = 90. c = (6) Å γ = 90. Volume 12,118(4) Å 3 Z 4 Density (calculated) g cm 3 Absorption coefficient mm 1 F(000) 3,964 Crystal size mm 3 Theta range for data collection 2.03 to Index ranges 19 h 20, 34 k 28, 41 l 36 Reflections collected 85,762 Independent reflections 27,659 [R int = ] Completeness to theta 98.9% Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 27,659 / 1 / 1,280 Goodness-of-fit on F Final R indices [I>2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e Å 3 CCDC reference number CCDC nature chemistry

23 supplementary information Table S3. Selected bond distances, bond angles, and dihedral angles of the crystal structures of (±)-DH2 BNaB BMAmm + and (±)-DH2 BB 2 (BMAmm + ) 2 (±)-DH2 BNaB BMAmm + (±)-DH2 BB 2 (BMAmm + ) 2 bond distance (Å) bond angle ( ) (±)-2 BNaB 2 (±)-2 BB C a -O a -B O 1 -B C b -O b -B O 2 -B O 3 -B 2 -O O a -B O 3 -B 2 -O c O b -B O 3 -B 2 -O d O 3 -B O 4 -B 2 -O c O 4 -B O 4 -B 2 -O d O c -B O c -B 2 -O d O d -B C 3 -O 3 -B O 2 -Na C 4 -O 4 -B O b -Na C c -O c -B O 3 -Na C d -O d -B O c -Na dihedral angle ( ) B 1 -B R 1 -R bond angle ( ) R 2 -R O 1 -B 1 -O R 3 -R O 1 -B 1 -O a R 4 -R O 1 -B 1 -O b R 5 -R O 2 -B 1 -O a R a -R b O 2 -B 1 -O b R b -R c O a -B 1 -O b R c -R d C 1 -O 1 -B R d -R e C 2 -O 2 -B R e -R f nature chemistry 23

24 supplementary information gcosy Spectrum of DH2 BB 2 (Na + 221) 2 Figure S MHz gcosy spectrum of DH2 BB 2 (Na + 221) 2 (CD 3 CN, 25 C, 0.7 mm). 24 nature chemistry

25 supplementary information Figure S15. Partial 500 MHz gcosy spectrum of DH2 BB 2 (Na + 221) 2 (CD 3 CN, 25 C, 0.7 mm). nature chemistry 25

26 supplementary information ROESY Spectrum of DH2 BB 2 (Na + 221) 2 Figure S MHz ROESY spectrum of DH2 BB 2 (Na + 221) 2 (CD 3 CN, 25 C, 0.7 mm, mixing time = 0.8 s). 26 nature chemistry

27 supplementary information Figure S17. Partial 500 MHz ROESY spectrum of DH2 BB 2 (Na + 221) 2 (CD 3 CN, 25 C, 0.7 mm, mixing time = 0.8 s). nature chemistry 27

28 supplementary information Figure S18. Partial 500 MHz ROESY spectrum of DH2 BB 2 (Na + 221) 2 (CD 3 CN, 25 C, 0.7 mm, mixing time = 0.8 s). 28 nature chemistry

29 supplementary information 1 H NMR Spectra of H 4 L2, DH2 BNaB Na +, and DH2 BB 2 (Na + 221) 2 Figure S19. Partial 500 MHz 1 H NMR spectra of H 4 L2 (red), DH2 BNaB Na + (blue), and DH2 BB 2 (Na + 221) 2 (green) (CD 3 CN, 25 C). nature chemistry 29

30 supplementary information 1 H NMR Spectra of 221, Na + 221, and DH2 BB 2 (Na + 221) 2 Figure S MHz DH2 BB 2 (Na + 221) 2 (black) (CD 3 CN, 25 C). 1 H NMR spectra of 221 (red), Na (blue), and 30 nature chemistry

31 supplementary information Interconversion between (+)-DH2 BNaB TBAmm + using Na + ion and (+)-DH2 BB 2 TBAmm + Na Figure S21. 1 H NMR spectra of (a) (+)-DH2 BNaB TBAmm + (red), (b) (a) (1.5 eq) (blue), and (c) (b) + NaPF 6 (1.5 eq) (green) (CD 3 CN, 25 C, 0.28 mm). nature chemistry 31

32 supplementary information Determination of the Binding Constant of (+)-DH2 BB 2 X 2+ to Na + ion The binding constant of (+)-DH2 BB 2 X 2+ to Na + ion was determined by the competitive binding titrations by use of dicyclohexano-18-crown-6 ether (DC18C6), since it is very high and beyond the detection limit of 1 H NMR spectroscopy. The competitive binding equilibrium between DH2 BB 2 X 2+ and DC18C6 is described as equation (1), DH2 BNaB X + + DC18C6 DH2 BB 2 X 2+ + Na + DC18C6, K rel = [DH2 BB 2 X 2+ ][Na + DC18C6]/([DH2 BNaB X + ][DC18C6]) = K C /K B (1) where K B and K C are the binding constants of DH2 BB 2 X 2+ and DC18C6 to Na + ion expressed by the following equations, (2) and (3), respectively. DH2 BB 2 X 2+ + Na + DH2 BNaB X +, K B = [DH2 BNaB X + ]/([DH2 BB 2 X 2+ ][Na + ]) (2) DC18C6 + Na + Na + DC18C6, K C = [Na + DC18C6]/([DC18C6][Na + ]) (3) Increasing amounts of DC18C6 were added into a solution of (+)-DH2 BNaB TBAmm + in CD 3 CN ( M, 64% e.e.), and their 1 H NMR spectra were recorded at 25 C after each addition. The concentrations of (+)-DH2 BNaB and (+)-DH2 BB 2 were determined by the integral ratio of the signals, and plots of the concentration of DH2 2 BB versus the total amount of added DC18C6 gave a binding isotherm as shown in Figure S22. The data were fitted to the following equation by the least-squares curve-fitting methods: [DH2 2 BB ] = [(B 0 +C 0 ) {(B 0 +C 0 ) 2 4(1 1/K rel )B 0 C 0 } 1/2 ]/{2(1 1/K rel )} (4), where B 0 and C 0 are the initial concentration of (+)-DH2 BNaB and the total amount of added DC18C6, respectively. The competitive binding constant, K rel, was determined to be (7.94 ± 0.21) 10 2, from which the binding constant of the extended helicate, DH2 2 BB, to Na + ion was calculated at M 1 in acetonitrile at 25 C by using the K C value of M 1 in acetonitrile at 25 C reported by Buschmann nature chemistry

33 supplementary information Figure S22. Plot of the concentration of DH2 BB 2 versus the total amount of added DC18C6 in the competitive binding titration. The red solid line represents the curve-fitting result. nature chemistry 33

34 supplementary information Temperature Effect on CD and Absorption Spectra of (+)-DH2 BNaB and (+)-DH2 BB 2 Figure S23. CD and absorption spectra (CH 3 CN, 25 C, cell length = 1.0 mm) of (a) (+)-DH2 BNaB TBAmm + (0.056 mm, 64% e.e.) and (b) (+)-DH2 BB 2 TBAmm + Na (0.055 mm, 64% e.e.) at various temperatures. 34 nature chemistry

35 supplementary information Interconversion between (+)-DH2 BNaB and (+)-DH2 BB 2 using Li + or K + ion Figure S24. CD and absorption spectral changes (CH 3 CN, 25 C, cell length = 0.2 mm) of (a) (+)-DH2 BNaB TBAmm + (0.28 mm, 64% e.e.) (i) before (blue) and (ii) after the addition of cryptand [2.2.1] (2.8 eq, red), and (iii) further addition of LiPF 6 (2.8 eq, dotted black) and (iv) cryptand [2.1.1] (green, 8.4 eq), and (b) (+)-DH2 BNaB TBAmm + (0.28 mm, 64% e.e.) (i) before (blue) and (ii) after the addition of cryptand [2.2.1] (3.0 eq, red), and (iii) further addition of KPF 6 (3.5 eq, dotted black) and (iv) cryptand [2.2.2] (green, 6.0 eq). nature chemistry 35

36 supplementary information Stopped-Flow CD Measurements for the Extension and Contraction Events Figure S25. Time traces of the changes in CD and absorption intensities at 240 nm in the (a) extension and (b) contraction events of the helicates measured in acetonitrile at 22 C. Stopped-flow measurements were performed using a JASCO J-820 spectropolarimeter with an SFS-492 stopped-flow attachment. Solutions of (+)-DH2 BNaB TBAmm + (0.152 mm, 64% e.e.) and 221 (0.456 mm) (a), or (+)-DH2 BB 2 TBAmm + (Na + 221) (0.102 mm (prepared from mm of (+)-DH2 BNaB TBAmm + (64% e.e.) and mm of 221) and NaPF 6 (0.456 mm) (b) were loaded in 10-mL syringes equipped with the attachment. Same volumes (50 μl each) of the solutions were mixed at a flow rate of 5 ml/msec at 22 C, and the changes in the intensities of the CD and absorption at 240 nm were monitored. The data for the extension were fit to the equation (1) based on a pseudo-second order kinetics by the nonlinear least-squares curve-fitting method to yield a k ext of (5.38 ± 0.05) 10 3 M 1 s 1 (see the solid black line in Fig. S25a). CD = α[dh2 BNaB ] 0 + (γ α)([221] 0 ([221] 0 )exp{([221] 0 [DH2 BNaB ] 0 )kt})/(1 ([221] 0 /[DH2 BNaB ] 0 )exp{([221] 0 [DH2 BNaB ] 0 )kt}) eq. (1), where α and γ are the ellipticities per concentration of DH2 BNaB and DH2 2 BB, respectively. In contrast, the contraction event was too fast to follow under the present experimental conditions, indicating that the contraction might finish at least within the dead time of 7.8 msec. Given that the half-life time (τ) is shorter than 7.8 msec, the pseudo-second order rate 36 nature chemistry

37 supplementary information constant for the contraction was estimated to be higher than a k cont of M 1 s 1, according to the equation (2) derived from the equation (1). k = ln[(2[napf 6 ] 0 [DH2 BB 2 ] 0 )/[NaPF 6 ] 0 ]/{([NaPF 6 ] 0 [DH2 BB 2 ] 0 )τ} eq. (2) 4. Supporting References 1. Katagiri, H., Miyagawa, T., Furusho, Y. & Yashima, E. Synthesis and optical resolution of a double helicate consisting of ortho-linked hexaphenol strands bridged by spiroborates. Angew. Chem. Int. Ed. 45, , (2006). 2. Demir, A. S., Reis, O. & Emrullahoglu, M. Role of copper species in the oxidative dimerization of arylboronic acids: Synthesis of symmetrical biaryls. J. Org. Chem. 68, (2003). 3. Bruker. SMART Version 5.624: Program for collecting frames of data, indexing reflection, and determination of lattice parameters; Bruker AXS, Inc., Madison, Wisconsin, USA (2000). 4. Bruker, SAINT Version 6.02: Program for integration of the intensity of reflections and scaling; Bruker AXS, Inc., Madison, Wisconsin, USA (2000). 5. Sheldrick, G. M. SADABS Version 2.03: Program for Performing Absorption Corrections to Single-Crystal X-ray Diffraction Patterns; University of Göttingen, Göttingen, Germany (2001). 6. SIR-97: Program for Crystal Structure Solution. Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. J. Appl. Crystallogr. 32, 155 (1999). 7. Sheldrick, G. M. SHELXL-97: Program for the Refinement of Crystal Structures; University of Göttingen, Göttingen, Germany (1997). 8. Bruker, SHELXTL Version 5.10: Suite of Programs for Crystal Structure Analysis, Incorporating Structure Solution (XS), Least-Squares Refinement (XL), and Graphics (XP); Bruker AXS, Inc., Madison, Wisconsin, USA (2000). 9. Buschmann, H.-J. J. Solution Chem. 17, (1988). nature chemistry 37

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany Carbene Activation of P 4 and Subsequent Derivatization Jason D. Masuda, Wolfgang W. Schoeller, Bruno Donnadieu, and Guy Bertrand * [*] Dr.

More information

Electronic Supplementary Information (ESI)

Electronic Supplementary Information (ESI) Electronic Supplementary Information (ESI) S1 Experimental Section: Materials and methods: All commercially available chemicals were used as supplied without further purification. The Q[5] was synthesized

More information

Reversible dioxygen binding on asymmetric dinuclear rhodium centres

Reversible dioxygen binding on asymmetric dinuclear rhodium centres Electronic Supporting Information for Reversible dioxygen binding on asymmetric dinuclear rhodium centres Takayuki Nakajima,* Miyuki Sakamoto, Sachi Kurai, Bunsho Kure, Tomoaki Tanase* Department of Chemistry,

More information

Supporting Information

Supporting Information Supporting Information Tris(allyl)indium Compounds: Synthesis and Structural Characterization Ilja Peckermann, Gerhard Raabe, Thomas P. Spaniol and Jun Okuda* Synthesis and characterization Figure S1:

More information

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Information Regiodivergent Heterocyclization: A Strategy for the Synthesis of Substituted Pyrroles and Furans Using α-formyl Ketene Dithioacetals as Common Precursors Ting Wu,

More information

Ziessel a* Supporting Information (75 pages) Table of Contents. 1) General Methods S2

Ziessel a* Supporting Information (75 pages) Table of Contents. 1) General Methods S2 S1 Chemistry at Boron: Synthesis and Properties of Red to Near-IR Fluorescent Dyes based on Boron Substituted Diisoindolomethene Frameworks Gilles Ulrich, a, * Sebastien Goeb a, Antoinette De Nicola a,

More information

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Information Selective Steroid Recognition by a Partially Bridged Resorcin[4]arene Cavitand Martina Cacciarini, a,b Vladimir A. Azov, a Paul Seiler, a Hermann Künzer c and François

More information

Syntheses and Structures of Mono-, Di- and Tetranuclear Rhodium or Iridium Complexes of Thiacalix[4]arene Derivatives

Syntheses and Structures of Mono-, Di- and Tetranuclear Rhodium or Iridium Complexes of Thiacalix[4]arene Derivatives Supplementary Information Syntheses and Structures of Mono-, Di- and Tetranuclear Rhodium or Iridium Complexes of Thiacalix[4]arene Derivatives Kenji Hirata, Toshiaki Suzuki, Ai Noya, Izuru Takei and Masanobu

More information

Electronic Supplementary Information for: Gram-scale Synthesis of a Bench-Stable 5,5 -Unsubstituted Terpyrrole

Electronic Supplementary Information for: Gram-scale Synthesis of a Bench-Stable 5,5 -Unsubstituted Terpyrrole Electronic Supplementary Information for: Gram-scale Synthesis of a Bench-Stable 5,5 -Unsubstituted Terpyrrole James T. Brewster II, a Hadiqa Zafar, a Matthew McVeigh, a Christopher D. Wight, a Gonzalo

More information

David L. Davies,*, 1 Charles E. Ellul, 1 Stuart A. Macgregor,*, 2 Claire L. McMullin 2 and Kuldip Singh. 1. Table of contents. General information

David L. Davies,*, 1 Charles E. Ellul, 1 Stuart A. Macgregor,*, 2 Claire L. McMullin 2 and Kuldip Singh. 1. Table of contents. General information Experimental Supporting Information for Experimental and DFT Studies Explain Solvent Control of C-H Activation and Product Selectivity in the Rh(III)-Catalyzed Formation of eutral and Cationic Heterocycles

More information

Reversible 1,2-Alkyl Migration to Carbene and Ammonia Activation in an NHC-Zirconium Complex.

Reversible 1,2-Alkyl Migration to Carbene and Ammonia Activation in an NHC-Zirconium Complex. Reversible 1,2-Alkyl Migration to Carbene and Ammonia Activation in an NHC-Zirconium Complex. Emmanuelle Despagnet-Ayoub, Michael K. Takase, Jay A. Labinger and John E. Bercaw Contents 1. Experimental

More information

Supporting Information for the Article Entitled

Supporting Information for the Article Entitled Supporting Information for the Article Entitled Catalytic Production of Isothiocyanates via a Mo(II) / Mo(IV) Cycle for the Soft Sulfur Oxidation of Isonitriles authored by Wesley S. Farrell, Peter Y.

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2017 Supporting Information Sulfonato-imino copper(ii) complexes : fast and general Chan-

More information

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Information Early-Late Heterobimetallic Rh-Ti and Rh-Zr Complexes via Addition of Early Metal Chlorides to Mono- and Divalent Rhodium Dan A. Smith and Oleg V. Ozerov* Department

More information

Prabhat Gautam, Bhausaheb Dhokale, Shaikh M. Mobin and Rajneesh Misra*

Prabhat Gautam, Bhausaheb Dhokale, Shaikh M. Mobin and Rajneesh Misra* Supporting Information Ferrocenyl BODIPYs: Synthesis, Structure and Properties Prabhat Gautam, Bhausaheb Dhokale, Shaikh M. Mobin and Rajneesh Misra* Department of Chemistry, Indian Institute of Technology

More information

Manganese-Calcium Clusters Supported by Calixarenes

Manganese-Calcium Clusters Supported by Calixarenes Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2014 Manganese-Calcium Clusters Supported by Calixarenes Rebecca O. Fuller, George A. Koutsantonis*,

More information

Aggregation-induced emission enhancement based on 11,11,12,12,-tetracyano-9,10-anthraquinodimethane

Aggregation-induced emission enhancement based on 11,11,12,12,-tetracyano-9,10-anthraquinodimethane Electronic Supplementary Information (ESI) Aggregation-induced emission enhancement based on 11,11,12,12,-tetracyano-9,10-anthraquinodimethane Jie Liu, ab Qing Meng, a Xiaotao Zhang, a Xiuqiang Lu, a Ping

More information

Synthesis of Vinyl Germylenes

Synthesis of Vinyl Germylenes Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Material for Synthesis of Vinyl Germylenes Małgorzata Walewska, Judith Baumgartner,*

More information

White Phosphorus is Air-Stable Within a Self-Assembled Tetrahedral Capsule

White Phosphorus is Air-Stable Within a Self-Assembled Tetrahedral Capsule www.sciencemag.org/cgi/content/full/324/5935/1697/dc1 Supporting Online Material for White Phosphorus is Air-Stable Within a Self-Assembled Tetrahedral Capsule Prasenjit Mal, Boris Breiner, Kari Rissanen,

More information

Supporting Information

Supporting Information Supporting Information Manuscript Title: Synthesis of Semibullvalene Derivatives via Co 2 (CO) 8 -Mediated Cyclodimerization of 1,4-Dilithio-1,3-butadienes Corresponding Author: Zhenfeng Xi Affiliations:

More information

Total Synthesis of Gonytolides C and G, Lachnone C, and. Formal Synthesis of Blennolide C and Diversonol

Total Synthesis of Gonytolides C and G, Lachnone C, and. Formal Synthesis of Blennolide C and Diversonol . This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Total Synthesis of Gonytolides C and G, Lachnone C, and Formal Synthesis

More information

Supporting Information Palladium-catalyzed, ortho-selective C-H halogenation of benzyl nitriles, aryl Weinreb amides and anilides.

Supporting Information Palladium-catalyzed, ortho-selective C-H halogenation of benzyl nitriles, aryl Weinreb amides and anilides. Supporting Information Palladium-catalyzed, ortho-selective C-H halogenation of benzyl nitriles, aryl Weinreb amides and anilides. Riki Das and Manmohan Kapur* Department of Chemistry, Indian Institute

More information

Crystal structure analysis of N,2-diphenylacetamide

Crystal structure analysis of N,2-diphenylacetamide International Journal of ChemTech Research CODEN (USA): IJCRGG ISSN: 0974-4290 Vol.9, No.04 pp 301-305, 2016 Crystal structure analysis of N,2-diphenylacetamide K. Elumalai 1, Subramaniyan Sathiyaraj 2,

More information

Supplementary Materials for

Supplementary Materials for www.advances.sciencemag.org/cgi/content/full/1/5/e1500304/dc1 Supplementary Materials for Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne click reaction This PDF file includes:

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 205 Supporting Information Synthesis and Structures of N-Arylcyano-β-diketiminate Zinc Complexes

More information

Supporting Information. DBU-Mediated Metal-Free Oxidative Cyanation of α-amino. Carbonyl Compounds: Using Molecular Oxygen as the Oxidant

Supporting Information. DBU-Mediated Metal-Free Oxidative Cyanation of α-amino. Carbonyl Compounds: Using Molecular Oxygen as the Oxidant Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information DBU-Mediated Metal-Free Oxidative Cyanation of α-amino

More information

Supplementary Figure S1 a, wireframe view of the crystal structure of compound 11. b, view of the pyridinium sites. c, crystal packing of compound

Supplementary Figure S1 a, wireframe view of the crystal structure of compound 11. b, view of the pyridinium sites. c, crystal packing of compound a b c Supplementary Figure S1 a, wireframe view of the crystal structure of compound 11. b, view of the pyridinium sites. c, crystal packing of compound 11. 1 a b c Supplementary Figure S2 a, wireframe

More information

Electronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones

Electronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones Electronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones Daisuke Uraguchi, Takaki Ito, Shinji Nakamura, and Takashi oi* Department of Applied Chemistry, Graduate School

More information

,

, 2013. 54, 6. 1115 1120 UDC 548.737:547.12 CHARACTERIZATION AND CRYSTAL STRUCTURES OF SOLVATED N -(4-HYDROXY-3-NITROBENZYLIDENE)-3-METHYLBENZOHYDRAZIDE AND N -(4-DIMETHYLAMINOBENZYLIDENE)-3-METHYLBENZOHYDRAZIDE

More information

Halogen bonded dimers and ribbons from the self-assembly of 3-halobenzophenones Patricia A. A. M. Vaz, João Rocha, Artur M. S. Silva and Samuel Guieu

Halogen bonded dimers and ribbons from the self-assembly of 3-halobenzophenones Patricia A. A. M. Vaz, João Rocha, Artur M. S. Silva and Samuel Guieu Electronic Supplementary Material (ES) for CrystEngComm. This journal is The Royal Society of Chemistry 27 Halogen bonded dimers and ribbons from the self-assembly of -halobenzophenones Patricia A. A.

More information

Supporting Information

Supporting Information Supporting Information New Hexaphosphane Ligands 1,3,5-C 6 H 3 {p-c 6 H 4 N(PX 2 ) 2 } 3 [X = Cl, F, C 6 H 3 OMe(C 3 H 5 )]: Synthesis, Derivatization and, Palladium(II) and Platinum(II) Complexes Sowmya

More information

Supplementary Information

Supplementary Information Supplementary Information Eco-Friendly Synthesis of 2,3-Dihydroquinazolin-4(1H)-ones Catalyzed by FeCl 3 /Al 2 O 3 and Analysis of Large 1 H NMR Diastereotopic Effect Isabel Monreal, a Mariano Sánchez-Castellanos,

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany Crystal-to-Crystal Transformation between Three Cu(I) Coordination Polymers and Structural Evidence for Luminescence Thermochromism Tae Ho

More information

Structural Elucidation of Sumanene and Generation of its Benzylic Anions

Structural Elucidation of Sumanene and Generation of its Benzylic Anions Structural Elucidation of Sumanene and Generation of its Benzylic Anions idehiro Sakurai, Taro Daiko, iroyuki Sakane, Toru Amaya, and Toshikazu irao Department of Applied Chemistry, Graduate School of

More information

Redox-Responsive Complexation between a. Pillar[5]arene with Mono ethylene oxide Substituents. and Paraquat

Redox-Responsive Complexation between a. Pillar[5]arene with Mono ethylene oxide Substituents. and Paraquat Redox-Responsive Complexation between a Pillar[5]arene with Mono ethylene oxide Substituents and Paraquat Xiaodong Chi, Min Xue, Yong Yao and Feihe Huang* MOE Key Laboratory of Macromolecular Synthesis

More information

Supporting Information

Supporting Information Submitted to Cryst. Growth Des. Version 1 of August 22, 2007 Supporting Information Engineering Hydrogen-Bonded Molecular Crystals Built from 1,3,5-Substituted Derivatives of Benzene: 6,6',6''-(1,3,5-Phenylene)tris-1,3,5-triazine-2,4-diamines

More information

Supplementary Material (ESI) for CrystEngComm. An ideal metal-organic rhombic dodecahedron for highly efficient

Supplementary Material (ESI) for CrystEngComm. An ideal metal-organic rhombic dodecahedron for highly efficient Supplementary Material (ESI) for CrystEngComm An ideal metal-organic rhombic dodecahedron for highly efficient adsorption of dyes in an aqueous solution Yuan-Chun He, Jin Yang,* Wei-Qiu Kan, and Jian-Fang

More information

Binuclear Rare-Earth Polyhydride Complexes Bearing both

Binuclear Rare-Earth Polyhydride Complexes Bearing both Supporting Information Binuclear Rare-Earth Polyhydride Complexes Bearing both Terminal and Bridging Hydride Ligands Jianhua Cheng, Haiyu Wang, Masayoshi Nishiura and Zhaomin Hou* S1 Contents Experimental

More information

1,4-Dihydropyridyl Complexes of Magnesium: Synthesis by Pyridine. Insertion into the Magnesium-Silicon Bond of Triphenylsilyls and

1,4-Dihydropyridyl Complexes of Magnesium: Synthesis by Pyridine. Insertion into the Magnesium-Silicon Bond of Triphenylsilyls and Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 Electronic Supporting Information 1,4-Dihydropyridyl Complexes of Magnesium: Synthesis

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2015 Supporting Information Single-Crystal-to-Single-Crystal Transformation of an Anion Exchangeable

More information

Active Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes

Active Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes Supplementary Information Active Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes Galyna Dubinina, Hideki Furutachi, and David A. Vicic * Department of Chemistry, University of Hawaii,

More information

1G (bottom) with the phase-transition temperatures in C and associated enthalpy changes (in

1G (bottom) with the phase-transition temperatures in C and associated enthalpy changes (in Supplementary Figure 1. Optical properties of 1 in various solvents. UV/Vis (left axis) and fluorescence spectra (right axis, ex = 420 nm) of 1 in hexane (blue lines), toluene (green lines), THF (yellow

More information

Juan Manuel Herrera, Enrique Colacio, Corine Mathonière, Duane Choquesillo-Lazarte, and Michael D. Ward. Supporting information

Juan Manuel Herrera, Enrique Colacio, Corine Mathonière, Duane Choquesillo-Lazarte, and Michael D. Ward. Supporting information Cyanide-bridged tetradecanuclear Ru II 3M II 11 clusters (M II = Zn II and Cu II ) based on the high connectivity building block [Ru 3 (HAT)(CN) 12 ] 6+ : structural and photophysical properties Juan Manuel

More information

Hassan Osseili, Debabrata Mukherjee, Klaus Beckerle, Thomas P. Spaniol, and Jun Okuda*

Hassan Osseili, Debabrata Mukherjee, Klaus Beckerle, Thomas P. Spaniol, and Jun Okuda* Supporting Information Me6TREN-Supported Alkali Metal Hydridotriphenylborates [(L)M][HBPh3] (M = Li, Na, K): Synthesis, Structure, and Reactivity Hassan Osseili, Debabrata Mukherjee, Klaus Beckerle, Thomas

More information

ph-responsive assembly and disassembly of a supramolecular cryptand-based pseudorotaxane driven by π-π stacking interaction

ph-responsive assembly and disassembly of a supramolecular cryptand-based pseudorotaxane driven by π-π stacking interaction ph-responsive assembly and disassembly of a supramolecular cryptand-based pseudorotaxane driven by π-π stacking interaction Xuzhou Yan, Mingming Zhang, Peifa Wei, Bo Zheng, Xiaodong Chi, Xiaofan Ji, and

More information

Stabilization of a Reactive Polynuclear Silver Carbide Cluster through the Encapsulation within Supramolecular Cage

Stabilization of a Reactive Polynuclear Silver Carbide Cluster through the Encapsulation within Supramolecular Cage Supporting Information Stabilization of a Reactive Polynuclear Silver Carbide Cluster through the Encapsulation within Supramolecular Cage Cai-Yan Gao, Liang Zhao,* and Mei-Xiang Wang* The Key Laboratory

More information

Nanocrystalline Magnesium Oxide-Stabilized Palladium(0): An Efficient and Reusable Catalyst for the Synthesis of N-(2- pyridyl)indoles

Nanocrystalline Magnesium Oxide-Stabilized Palladium(0): An Efficient and Reusable Catalyst for the Synthesis of N-(2- pyridyl)indoles Electronic Supplementary Material (ESI) for ew Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre ational de la Recherche Scientifique 2015 Supplementary Material (ESI)

More information

Supporting Information

Supporting Information Supporting Information Calix[4, 5]tetrolarenes: A New Family of Macrocycles Yossi Zafrani* and Yoram Cohen* School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Ramat Aviv 69978,

More information

Supporting Information

Supporting Information Remarkably Variable Reaction Modes of Frustrated Lewis Pairs with Non-Conjugated Terminal Diacetylenes Chao Chen, Roland Fröhlich, Gerald Kehr, Gerhard Erker Organisch-Chemisches Institut, Westfälische

More information

Selective total encapsulation of the sulfate anion by neutral nano-jars

Selective total encapsulation of the sulfate anion by neutral nano-jars Supporting Information for Selective total encapsulation of the sulfate anion by neutral nano-jars Isurika R. Fernando, Stuart A. Surmann, Alexander A. Urech, Alexander M. Poulsen and Gellert Mezei* Department

More information

Enantioselectivity switch in copper-catalyzed conjugate addition. reaction under influence of a chiral N-heterocyclic carbene-silver complex

Enantioselectivity switch in copper-catalyzed conjugate addition. reaction under influence of a chiral N-heterocyclic carbene-silver complex Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supplementary Information Enantioselectivity switch in copper-catalyzed conjugate addition

More information

Supporting Information

Supporting Information Selective Hg 2+ sensing behaviors of rhodamine derivatives with extended conjugation based on two successive ring-opening processes Chunyan Wang a,b and Keith Man-Chung Wong a,b * a Department of Chemistry,

More information

Halogen halogen interactions in diiodo-xylenes

Halogen halogen interactions in diiodo-xylenes Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2016 Electronic Supplementary Information (ESI) for CrystEngComm. This journal is The Royal Society

More information

A Clipped [3]Rotaxane Derived From Bis-nor-seco-Cucurbit[10]uril

A Clipped [3]Rotaxane Derived From Bis-nor-seco-Cucurbit[10]uril A Clipped [3]Rotaxane Derived From Bis-nor-seco-Cucurbit[10]uril Supplementary Information by James B. Wittenberg, Matthew G. Costales, Peter Y. Zavalij, and Lyle Isaacs* Department of Chemistry and Biochemistry,

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Supporting Information Unmasking Representative Structures of TMP-Active Hauser and Turbo Hauser Bases Pablo García-Álvarez, David V. Graham,

More information

Molecular Imaging of Labile Iron(II) Pools in Living Cells with a Turn-on Fluorescent Probe

Molecular Imaging of Labile Iron(II) Pools in Living Cells with a Turn-on Fluorescent Probe Supporting Information for Molecular Imaging of Labile Iron(II) Pools in Living Cells with a Turn-on Fluorescent Probe Ho Yu Au-Yeung, Jefferson Chan, Teera Chantarojsiri and Christopher J. Chang* Departments

More information

Electronic Supplementary Information. Pd(diimine)Cl 2 Embedded Heterometallic Compounds with Porous Structures as Efficient Heterogeneous Catalysts

Electronic Supplementary Information. Pd(diimine)Cl 2 Embedded Heterometallic Compounds with Porous Structures as Efficient Heterogeneous Catalysts Electronic Supplementary Information Pd(diimine)Cl 2 Embedded Heterometallic Compounds with Porous Structures as Efficient Heterogeneous Catalysts Sheng-Li Huang, Ai-Quan Jia and Guo-Xin Jin* Experimental

More information

The oxide-route for the preparation of

The oxide-route for the preparation of Supporting Information for: The oxide-route for the preparation of mercury(ii) N-heterocyclic carbene complexes. Simon Pelz and Fabian Mohr* Fachbereich C-Anorganische Chemie, Bergische Universität Wuppertal,

More information

The CB[n] Family: Prime Components for Self-Sorting Systems Supporting Information

The CB[n] Family: Prime Components for Self-Sorting Systems Supporting Information The CB[n] Family: Prime Components for Self-Sorting Systems Supporting Information by Simin Liu, Christian Ruspic, Pritam Mukhopadhyay,Sriparna Chakrabarti, Peter Y. Zavalij, and Lyle Isaacs* Department

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany A New Melt Approach to the Synthesis of catena- Phosphorus Dications to Access the First Derivatives of 2+ ** [P 6 Ph 4 R 4 ] Jan J. Weigand*,

More information

High-performance Single-crystal Field Effect Transistors of Pyreno[4,5-a]coronene

High-performance Single-crystal Field Effect Transistors of Pyreno[4,5-a]coronene Electronic Supplementary Information High-performance Single-crystal Field Effect Transistors of Pyreno[4,5-a]coronene Experimental details Synthesis of pyreno[4,5-a]coronene: In 1960 E. Clar et.al 1 and

More information

Hydrophobic Ionic Liquids with Strongly Coordinating Anions

Hydrophobic Ionic Liquids with Strongly Coordinating Anions Supporting material Hydrophobic Ionic Liquids with Strongly Coordinating Anions Hasan Mehdi, Koen Binnemans*, Kristof Van Hecke, Luc Van Meervelt, Peter Nockemann* Experimental details: General techniques.

More information

Spain c Departament de Química Orgànica, Universitat de Barcelona, c/ Martí I Franqués 1-11, 08080, Barcelona, Spain.

Spain c Departament de Química Orgànica, Universitat de Barcelona, c/ Martí I Franqués 1-11, 08080, Barcelona, Spain. a Institute of Chemical Research of Catalonia, Av. Països Catalans, 16, 43007 Tarragona, Spain. b Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, E-08193 Barcelona, Spain

More information

Electronic Supplementary Information (ESI)

Electronic Supplementary Information (ESI) Electronic Supplementary Information (ESI) Crystal Engineering of Multiple-Component Organic Solids: Pharmaceutical Cocrystals of Tadalafil with Persistent Hydrogen Bonding Motifs David R. Weyna, a Miranda

More information

Derivatives. Republic. Supporting Information. Index. General Considerations. Experimental Procedures and Spectroscopic Data

Derivatives. Republic. Supporting Information. Index. General Considerations. Experimental Procedures and Spectroscopic Data Synthesis of Hexahelicene and 1-Methoxyhexahelicene via Cycloisomerization of Biphenylyl-Naphthalene Derivatives Jan Storch *, Jan Sýkora, Jan Čermák, Jindřich Karban, Ivana Císařová and Aleš Růžička Institute

More information

Supporting Information

Supporting Information Supporting Information Synthesis of H-Indazoles from Imidates and Nitrosobenzenes via Synergistic Rhodium/Copper Catalysis Qiang Wang and Xingwei Li* Dalian Institute of Chemical Physics, Chinese Academy

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2015 A rare case of a dye co-crystal showing better dyeing performance Hui-Fen Qian, Yin-Ge Wang,

More information

Supporting Information (98 pages)

Supporting Information (98 pages) Supporting Information (98 pages) Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal Organic Framework-177 Yue-Biao Zhang, Hiroyasu Furukawa,

More information

Synthetic, Structural, and Mechanistic Aspects of an Amine Activation Process Mediated at a Zwitterionic Pd(II) Center

Synthetic, Structural, and Mechanistic Aspects of an Amine Activation Process Mediated at a Zwitterionic Pd(II) Center Synthetic, Structural, and Mechanistic Aspects of an Amine Activation Process Mediated at a Zwitterionic Pd(II) Center Supporting Information Connie C. Lu and Jonas C. Peters* Division of Chemistry and

More information

Supporting Information

Supporting Information Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013 Tuning the Lewis Acidity of Boranes in rustrated Lewis Pair Chemistry: Implications for the Hydrogenation of Electron-Poor

More information

Simple Solution-Phase Syntheses of Tetrahalodiboranes(4) and their Labile Dimethylsulfide Adducts

Simple Solution-Phase Syntheses of Tetrahalodiboranes(4) and their Labile Dimethylsulfide Adducts Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Supporting Information for: Simple Solution-Phase Syntheses of Tetrahalodiboranes(4) and their

More information

Electronic Supporting Information

Electronic Supporting Information Electronic Supporting Information Solid-State Coexistence of {Zr 12 } and {Zr 6 } Zirconium Oxocarboxylate Clusters Iurie L. Malaestean, Meliha Kutluca Alıcı, Claire Besson, Arkady Ellern and Paul Kögerler*

More information

Stereoselective Synthesis of (-) Acanthoic Acid

Stereoselective Synthesis of (-) Acanthoic Acid 1 Stereoselective Synthesis of (-) Acanthoic Acid Taotao Ling, Bryan A. Kramer, Michael A. Palladino, and Emmanuel A. Theodorakis* Department of Chemistry and Biochemistry, University of California, San

More information

Enantioselective Conjugate Addition of 3-Fluoro-Oxindoles to. Vinyl Sulfone: An Organocatalytic Access to Chiral. 3-Fluoro-3-Substituted Oxindoles

Enantioselective Conjugate Addition of 3-Fluoro-Oxindoles to. Vinyl Sulfone: An Organocatalytic Access to Chiral. 3-Fluoro-3-Substituted Oxindoles Enantioselective Conjugate Addition of 3-Fluoro-Oxindoles to Vinyl Sulfone: An Organocatalytic Access to Chiral 3-Fluoro-3-Substituted Oxindoles Xiaowei Dou and Yixin Lu * Department of Chemistry & Medicinal

More information

Phosphirenium-Borate Zwitterion: Formation in the 1,1-Carboboration Reaction of Phosphinylalkynes. Supporting Information

Phosphirenium-Borate Zwitterion: Formation in the 1,1-Carboboration Reaction of Phosphinylalkynes. Supporting Information Phosphirenium-Borate Zwitterion: Formation in the 1,1-Carboboration Reaction of Phosphinylalkynes Olga Ekkert, Gerald Kehr, Roland Fröhlich and Gerhard Erker Supporting Information Experimental Section

More information

Supporting Information

Supporting Information Supporting Information Organocatalytic Enantioselective Formal Synthesis of Bromopyrrole Alkaloids via Aza-Michael Addition Su-Jeong Lee, Seok-Ho Youn and Chang-Woo Cho* Department of Chemistry, Kyungpook

More information

Highly Luminescent -Conjugated Dithienometalloles: Photophysical Properties and Application to Organic Light-Emitting Diodes

Highly Luminescent -Conjugated Dithienometalloles: Photophysical Properties and Application to Organic Light-Emitting Diodes Electronic Supplementary Information (ESI) Highly Luminescent -Conjugated Dithienometalloles: Photophysical Properties and Application to Organic Light-Emitting Diodes Ryosuke Kondo, a Takuma Yasuda,*

More information

Supporting Information

Supporting Information Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2014. Supporting Information for Advanced Optical Materials, DOI: 10.1002/adom.201400078 Staggered Face-to-Face Molecular Stacking as

More information

Supporting Information

Supporting Information Supporting Information One-Pot Access to Benzo[a]carbazoles via Palladium(II)-Catalyzed Hetero- and Carboannulations Moumita Jash, Bimolendu Das, and Chinmay Chowdhury* Organic & dicinal Chemistry Division,

More information

Supporting Information. for

Supporting Information. for Supporting Information for "Inverse-Electron-Demand" Ligand Substitution in Palladium(0) Olefin Complexes Shannon S. Stahl,* Joseph L. Thorman, Namal de Silva, Ilia A. Guzei, and Robert W. Clark Department

More information

Copper Mediated Fluorination of Aryl Iodides

Copper Mediated Fluorination of Aryl Iodides Copper Mediated Fluorination of Aryl Iodides Patrick S. Fier and John F. Hartwig* Department of Chemistry, University of California, Berkeley, California 94720, United States. Supporting Information Table

More information

Cu(I)-MOF: naked-eye colorimetric sensor for humidity and. formaldehyde in single-crystal-to-single-crystal fashion

Cu(I)-MOF: naked-eye colorimetric sensor for humidity and. formaldehyde in single-crystal-to-single-crystal fashion Supporting Information for Cu(I)-MOF: naked-eye colorimetric sensor for humidity and formaldehyde in single-crystal-to-single-crystal fashion Yang Yu, Xiao-Meng Zhang, Jian-Ping Ma, Qi-Kui Liu, Peng Wang,

More information

b = (13) Å c = (13) Å = (2) V = (19) Å 3 Z =2 Data collection Refinement

b = (13) Å c = (13) Å = (2) V = (19) Å 3 Z =2 Data collection Refinement organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 b = 12.4861 (13) Å c = 12.9683 (13) Å = 90.748 (2) V = 1051.10 (19) Å 3 Z =2 Mo K radiation = 3.87 mm 1 T = 193

More information

SUPPORTING INFORMATION

SUPPORTING INFORMATION SUPPORTING INFORMATION Table of Contents S1 1. General materials and methods S2 2. Syntheses of {Pd 84 } and {Pd 17 } S3-S4 3. MS studies of {Pd 84 }, {Pd 17 } and the two-component reactions S5-S6 4.

More information

Copyright WILEY-VCH Verlag GmbH, D Weinheim, 2000 Angew. Chem Supporting Information For Binding Cesium Ion with Nucleoside Pentamers.

Copyright WILEY-VCH Verlag GmbH, D Weinheim, 2000 Angew. Chem Supporting Information For Binding Cesium Ion with Nucleoside Pentamers. Copyright WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 Angew. Chem. 2000 Supporting Information For Binding Cesium Ion with Nucleoside Pentamers. Templated Self-Assembly of an Isoguanosine Decamer.**

More information

Supporting Information. for. Advanced Functional Materials, adfm Wiley-VCH 2007

Supporting Information. for. Advanced Functional Materials, adfm Wiley-VCH 2007 Supporting Information for Advanced Functional Materials, adfm.200601202 Wiley-VCH 2007 69451 Weinheim, Germany [Supporting Information] Optical Sensor Based on Nanomaterial for the Selective Detection

More information

Supporting Information

Supporting Information Supporting Information Heteroligand o-semiquinonato-formazanato cobalt complexes Natalia A. Protasenko, Andrey I. Poddel sky,*, Artem S. Bogomyakov, Georgy K. Fukin, Vladimir K. Cherkasov G.A. Razuvaev

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2016 Supporting Information Over or under: Hydride attack at the metal versus the coordinated

More information

Electronic Supplementary Information

Electronic Supplementary Information Electronic Supplementary Information [7]-Helicene: A Chiral Molecular Tweezer for Silver(I) Salts. Matthew J. Fuchter, a* Julia Schaefer, b Dilraj K. Judge, a Benjamin Wardzinski, a Marko Weimar, a Ingo

More information

metal-organic compounds

metal-organic compounds metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 Dichloridotris(trimethylphosphine)- nickel(ii) Ruixia Cao, Qibao Wang and Hongjian Sun* School of Chemistry

More information

metal-organic compounds

metal-organic compounds metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 Poly[tetra-l-cyanido-dipyridinecadmium(II)zinc(II)] Sheng Li,* Kun Tang and Fu-Li Zhang College of Medicine,

More information

Small Molecule Crystallography Lab Department of Chemistry and Biochemistry University of Oklahoma 101 Stephenson Parkway Norman, OK

Small Molecule Crystallography Lab Department of Chemistry and Biochemistry University of Oklahoma 101 Stephenson Parkway Norman, OK Small Molecule Crystallography Lab Department of Chemistry and Biochemistry University of Oklahoma 101 Stephenson Parkway Norman, OK 73019-5251 Sample: KP-XI-cinnamyl-chiral alcohol Lab ID: 12040 User:

More information

b = (9) Å c = (7) Å = (1) V = (16) Å 3 Z =4 Data collection Refinement

b = (9) Å c = (7) Å = (1) V = (16) Å 3 Z =4 Data collection Refinement organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 8-Iodoquinolinium triiodide tetrahydrofuran solvate Jung-Ho Son and James D. Hoefelmeyer* Department of Chemistry,

More information

Reversible uptake of HgCl 2 in a porous coordination polymer based on the dual functions of carboxylate and thioether

Reversible uptake of HgCl 2 in a porous coordination polymer based on the dual functions of carboxylate and thioether Supplementary Information Reversible uptake of HgCl 2 in a porous coordination polymer based on the dual functions of carboxylate and thioether Xiao-Ping Zhou, a Zhengtao Xu,*,a Matthias Zeller, b Allen

More information

Department of Chemistry, Tianjin University, Tianjin , P. R. China Tel:

Department of Chemistry, Tianjin University, Tianjin , P. R. China   Tel: Electronic Supplementary Information Analysis of factors governing the formation of single-stranded helical coordination polymers from a macrocyclic metalloligand and Ca 2+, Mn 2+, Fe 2+, Co 2+, Ni 2+,

More information

Iron Complexes of a Bidentate Picolyl NHC Ligand: Synthesis, Structure and Reactivity

Iron Complexes of a Bidentate Picolyl NHC Ligand: Synthesis, Structure and Reactivity Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2016 Supplementary Information for Iron Complexes of a Bidentate Picolyl HC Ligand: Synthesis,

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 208 Supporting Information Cobalt-Catalyzed Regioselective Syntheses of Indeno[2,-c]pyridines

More information

Z =8 Mo K radiation = 0.35 mm 1. Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections

Z =8 Mo K radiation = 0.35 mm 1. Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 4-Amino-3-(4-pyridyl)-1,2,4-triazole- 5(4H)-thione Fang Zou, Wei-Min Xuan, Xue-Ming Fang and Hui Zhang* State

More information

Reversible Enolization of!-amino Carboxamides by Lithium Hexamethyldisilazide. Anne J. McNeil and David B. Collum*

Reversible Enolization of!-amino Carboxamides by Lithium Hexamethyldisilazide. Anne J. McNeil and David B. Collum* Reversible Enolization of!-amino Carboxamides by Lithium Hexamethyldisilazide Anne J. McNeil and David B. Collum* Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca,

More information

Supporting Information. for. Angew. Chem. Int. Ed Wiley-VCH 2004

Supporting Information. for. Angew. Chem. Int. Ed Wiley-VCH 2004 Supporting Information for Angew. Chem. Int. Ed. 246736 Wiley-VCH 24 69451 Weinheim, Germany 1 Challenges in Engineering Spin Crossover. Structures and Magnetic Properties of six Alcohol Solvates of Iron(II)

More information