Dynamic propeller conformation for the unprecedentedly high degree of chiral amplification of supramolecular helices

Unprecedentedly high degree of chiral amplification using dynamic propeller conformation of triphenylamine.


General
Materials and me Unless otherwise indicated, all starting materials were obtained from commercial suppliers (Wako Pure Chemical, Kanto, and TCI, etc.) and were used without purification. Methylene chloride, hexane, DMF, and Ethanol were distilled before use.
Methods: Visualization of synthesized compounds was accomplished with UV light, iodine vapor or by staining using base solution of cerium ammonium molybdate. Flash chromatography was carried out with Silica Gel 60 (230-400 mesh) from Wako Pure Chemical Industries, Ltd.
Recycling preparative high-performance liquid chromatography (HPLC) was performed using a YMC-GPC column on an YMC LC-Forte/R. 1 H and 13 C NMR spectra were recorded at 25 °C on a JEOL model JNM-ECA500 spectrometer, operating at 500 and 125 MHz, respectively, where chemical shifts (δ in ppm) were determined using tetramethylsilane as an internal reference. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry was performed in the reflector mode on a Brucker model autoflex TM speed spectrometer. Electronic absorption and circular dichroism (CD) spectra were recorded on a JASCO model V-670 UV/VIS/NIR spectrophotometer and a JASCO Type J-820 spectropolarimeter, respectively, using a quartz cell of 10 mm optical path length. Dynamic light scattering (DLS) measurements were performed with a Malvern type Zetasizer Nano ZSP at 25 °C using a quartz cell of 10 mm optical path length. Infrared spectra were recorded using a JASCO model FT/IR-610Plus Fourier transform infrared spectrometer. Vibrational circular dichroism (VCD) spectra were measured in a 0.5 mm BaF 2 cell with JASCO FVS-6000. All VCD spectra were collected for ca. 2-3 h at a resolution of 4 cm -1 . g-values used in this manuscript is calculated from the following equation.
where ε is molar ellipticity, A represents the conventional absorbance of nonpolarized light, A l and A r are the absorptions of left and right circularly polarized light, respectively. S1 S3

Synthesis of A, A -p ,
The solution was poured into ethanol (100 mL) to precipitate of a white solid. The residue was chromatographed on silica gel with CHCl 3 /EtOH (99/1 v/v) as an eluent, where the second fraction was collected and evaporated to dryness. The residue was subjected to recycling preparative HPLC (YMC LC-forte/R) with CHCl 3 as an eluent at a flow rate of 10 mL min -1 , where the first fraction was collected and evaporated to dryness under reduced pressure to give  5, 153.3, 144.3, 141.5, 132.9, 129.8, 124.4, 121.5, 105.7, 71.8, 67.8, 39.3, 37.4, 36.4, 29.8, 29.6, 28.0, 24.7, 22.6, 19.6 Figure S10. MALDI-TOF-MS spectrum of A using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Figure S11. MALDI-TOF-MS spectrum of A -p using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Supporting Information S25 Figure S12. MALDI-TOF-MS spectrum of A -m using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Figure S13. MALDI-TOF-MS spectrum of C 1m (S) using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Supporting Information S26 Figure S14. MALDI-TOF-MS spectrum of C 1p (S) using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Figure S15. MALDI-TOF-MS spectrum of C 1p (R) using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Supporting Information S27 Figure S16. MALDI-TOF-MS spectrum of C 2m,m (S) using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Figure S17. MALDI-TOF-MS spectrum of C 3 (S) using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation. Supporting Information S28 Figure S18. MALDI-TOF-MS spectrum of C 3 (R) using CHCA as a matrix. The peak due to [M -RCO + H] + became more intense when a larger laser power was applied. Therefore, the laser power was adjusted to be as small as possible in order to avoid fragmentation.

Theoretical Estimation of the MMP and HRP values
The MMP and HRP values were estimated using the data obtained from the sergeants and soldiers experiments with mixtures of A/C 3 (S). The g-values at 252 nm were converted into the dimensionless net helicity and fit to the least-squares model developed by van der Schoot. S8 The contour plot of the sum of squared residuals exhibited a narrow region with a minimum at σ = 6.3·10 -8 and ω = 0.68 ( Figure S19a), and the corresponding fit is shown in Figure S19b. At this point, a combination of HRP and MMP resulted in the best fit of the data. Comparison of the experimental data and the theoretical fitting curve for the net helicity obtained by the above model.   For elongation regime For nucleation regime Number-averaged degree of polymerization, <N n > h e : the molecular enthalpy, T e : the elongation temperature, φ n : the degree of aggregation, φ SAT : the parameter, K a : the dimensionless equilibrium constant of the activation step at T e . Supporting Information S46 Figure S36. Plots of the net helicity against the fraction of the sergeants for the mixtures of