Nagoya University, Chikusa-ku, Nagoya , Japan. Present Address: Department of Molecular and Macromolecular Chemistry,

Transcription

1 Supporting Information for: Chiral Template-Directed egio-, Diastereo-, and Enantioselective otodimerization of an Anthracene Derivative Assisted by Complementary AmidiniumCarboxylate Salt Bridge Formation Junki Tanabe, Daisuke Taura, aoki usaka, and Eiji Yashima*, Department of Molecular Design and Engineering, Graduate School of Engineering, agoya University, Chikusa-ku, agoya , Japan Present Address: Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, agoya University, Chikusa-ku, agoya , Japan. S1

2 Table of Contents 1. Instruments and Materials S3 2. Synthetic Procedures S4 3. General Procedures for otodimerization S6 4. Isolation of Stereoisomers of 1-Me, ptical esolution, and Structure Determination S7 5. otodimerization of 1 in the Presence of Chiral Templates: Isolation of otodimers, Methyl Esterification, and Enantiomeric Excess Determination S8 6. otodimerization of Monomers in the Absence of Template 6-1. otodimerization of Carboxylic Acid Methyl Ester Monomer (1-Me) (run 1, Table 1) S otodimerization of Carboxylic Acid Monomer (1) (run 2, Table 1) S11 7. otodimerization of 1 in the Presence of Amidine Templates 7-1. CD and Absorption Spectra of 1 in the Presence of Amidine Templates S otodimerization of 1 in the Presence of Monomeric Amidine ((,)-A) (run 3, Table 1) S otodimerization of 1 in the Presence of Dimeric Amidine Template ((,,,)-T1) (run 4, Table 1) S otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((,,S,S,,)-T2) (run 5, Table 1) S otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((S,S,S,S,S,S)-T3) (run 6, Table 1) S otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((,,,,,)-T4) (run 7, Table 1) S otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((,,S,S,,)-T5) (run 8, Table 1) S22 8. Spectroscopic Data S29 9. Supporting eferences S36 S2

3 1. Instruments and Materials Instruments The melting points were measured on a Yanaco MP-500D micromelting point apparatus (Yanako, Kyoto, Japan) and were uncorrected. The I spectra were recorded on a JASC FT/I- 680 spectrophotometer (JASC, Tokyo, Japan). The M spectra were measured on a Bruker Ascend 500 (Bruker Biospin, Billerica, MA) or a Varian 500AS (Varian, Palo Alto, CA) spectrometer operating at 500 Mz for 1 and 125 Mz for 13 C using a Teflon-valved M tube (5-mm (i.d.)) (orell Inc.). Chemical shifts are reported in parts per million ( ) downfield from tetramethylsilane () in CDCl3 or in benzene-d6 using a solvent residual peak as the internal standard. The absorption and CD spectra were measured in a or 0.1-cm quartz cell using a JASC V-570 spectrophotometer and a JASC J-820 or a JASC J-1500 spectropolarimeter, respectively. The temperature was controlled with a JASC PTC-423L apparatus. The photoirradiation ( > 400 nm) was performed using a 500 W xenon lamp (Ushio ptical Modulex SX-UI500XQ) through a cut-off filter (SIGMAKKI Co., Ltd.). The temperature during the photoirradiation was controlled using an ultra-cooling reactor (UC-150) (Techno Sigma Co., Ltd., kayama, Japan). The electrospray ionization (ESI) mass spectra were recorded using a JEL JMS-T100CS mass spectrometer (JEL, Akishima, Japan). The PLC separation of stereoisomeric photodimers was performed on a JASC PU-2080 liquid chromatograph equipped with an UVvisible (JASC MD-2010) detector. Two Inert SIL-100A columns (0.46 (i.d.) 25 cm, GL Sciences, Tokyo, Japan) or CSMSIL 5C18-MS-II and 5C18-A-II columns (0.46 (i.d.) 25 cm, acalai Tesque, Kyoto, Japan) were connected in series. The chiral PLC analyses were performed on a JASC PU-2080 liquid chromatograph equipped with UV-visible (JASC MD-2010) and CD (JASC CD-2095) detectors using a CIALPAK IB column (0.46 (i.d.) 25 cm, Daicel, saka, Japan). Materials All starting materials and dehydrated solvents were purchased from Aldrich (Milwaukee, WI), Wako Pure Chemical Industries (saka, Japan), and Tokyo Chemical Industry (Tokyo, Japan) unless otherwise noted. Silica gel (Si2) and aminopropyl-modified silica gel (-Si2) for the flash chromatography were purchased from Merck and Fuji Silysia Chemical Ltd. (Kusanagi, Japan), respectively. Compounds C-, S1 (,)-A-, S2 (S,S)-A-, S2 (S,S)-L, S3 (,,,)-T1, S1 (,,,,,)-T4, S3 and (,,S,S,,)-T5 S3 were prepared according to the previously reported methods. S3

4 2. Synthetic Procedures Scheme S1. Synthesis of carboxylic acid monomer (1). 1. Copper (I) iodide (3.79 mg, 19.9 µmol) was added to a solution of C- (100 mg, mmol), 2-bromoanthracene (256 mg, mmol), and tetrakis(triphenylphosphine)palladium(0) (23.0 mg, 19.9 µmol) in a TF-diisopropylamine mixture (1/1 (v/v), 10 ml) and the mixture was stirred at 75 C for 29 h. After evaporating the solvents, the residue was purified by column chromatography (Si2, n-hexane/etac = 1/0 to 4/1 (v/v)) to give pure 1 (45.9 mg, 34.0% yield) as a yellow solid. Mp: C. I (KBr, cm 1 ): 2157 ( C C), 1701 ( C=). 1 M (500 Mz, CDCl3, 25 C): δ 8.37 (s, 1, Ar), 8.34 (s, 1, Ar), 8.23 (s, 1, Ar), (m, 3, Ar), 7.66 (d, J = 8.4 z, 2, Ar), (m, 3, Ar), (m, 2, Ar), (m, 4, Ar), 7.35 (d, J = 8.4 z, 2, Ar), 2.42 (t, J = 7.1 z, 2, C CC2), (m, 2, C2), (m, 2, C2), (m, 4, C2), 0.90 (t, J = 7.1 z, 3, C3), 0.25 (s, 9, ). 13 C M (125 Mz, CDCl3, 25 C): δ 171.6, , , 139.8, 139.6, 132.2, , , , , , 131.8, 131.1, 130.7, 130.4, 128.6, 128.4, , , 128.2, 127.7, 126.4, 126.3, 126.0, 125.9, 125.8, 123.1, 122.9, 120.0, 104.8, 95.5, 93.1, 91.2, 90.1, 79.5, 31.4, 28.7, 28.6, 22.6, 19.5, 14.0, UV-vis (CDCl3): max (ε [M 1 cm 1 ]) = 396 (11,500), 375 (17,400), 357 (15,600) nm. MS (ESI ): m/z calcd for C48422Si (M ), ; found Scheme S2. Synthesis of carboxylic acid methyl ester monomer (1-Me). 1-Me. To a solution of 1 (4.4 mg, 6.5 µmol) in CCl3 (0.70 ml) and Me (0.30 ml) was added (trimethylsilyl)diazomethane (0.6 M in n-hexane, 32 µl, 19 µmol) at room temperature and the mixture was stirred at room temperature for 1 h. After evaporating the solvents, the residue was S4

5 purified by column chromatography (Si2, n-hexane/etac = 4/1 (v/v)) to afford 1-Me (4.2 mg, 95% yield) as a pale yellow solid. Mp: C. I (KBr, cm 1 ): 2157 ( C C), 1735 ( C=). 1 M (500 Mz, CDCl3, 25 C): δ 8.41 (s, 2, Ar), 8.24 (s, 1, Ar), (m, 3, Ar), 7.62 (d, J = 8.5 z, 2, Ar), (m, 5, Ar), (m, 4, Ar), 7.33 (d, J = 8.5 z, 2, Ar), 3.41 (s, 3, C3C2), 2.42 (t, J = 7.0 z, 2, C CC2), (m, 2, C2), (m, 2, C2), (m, 4, C2), 0.90 (t, J = 7.0 z, 3, C3), 0.27 (s, 9, ). 13 C M (125 Mz, CDCl3, 25 C): δ 169.2, 140.1, 139.9, 132.3, 132.2, 132.0, 131.9, 131.8, 131.7, 131.6, 131.2, 130.8, 128.5, 128.4, , , , 127.6, 126.4, 126.3, 125.9, , , 122.9, 122.7, 120.0, 104.8, 95.2, 92.9, 91.1, 90.1, 79.6, 52.0, 31.4, 28.7, 28.6, 22.6, 19.5, 14.1, UV-vis (CDCl3): max (ε [M 1 cm 1 ]) = 396 (11,500), 375 (17,400), 357 (15,600) nm. MS (ESI): m/z calcd for C49442Si (M ), ; found Scheme S3. Synthesis of amidine template (,,S,S,,)-T2. (,,S,S,,)-T2. Copper (I) iodide (3.73 mg, 19.6 µmol) was added to a solution of (,)-A- (236 mg, mmol), (S,S)-L (80.0 mg, mmol), and tetrakis(triphenylphosphine)palladium(0) (22.6 mg, 19.6 µmol) in a TF-diisopropylamine mixture (1/1 (v/v), 10 ml) and the mixture was stirred at 75 C for 13 h. After evaporating the solvents, the residue was purified by column chromatography (-Si2, n-hexane/etac = 1/0 to 9/1 (v/v)) to give pure (,,S,S,,)-T2 (122 mg, 43.0% yield) as a white solid. Mp: C. I (KBr, cm 1 ): 2157 ( C C), 1638 ( C=). 1 M (500 Mz, CDCl3, 25 C, as (,,S,S,,)- T2 (C3C2)2): δ (br, 4, ), 7.76 (t, J = 7.5 z, 2, Ar), (m, 4, Ar), (m, 20, Ar), (m, 8, Ar), 7.01 (s, 2, Ar), 6.71 (d, J = 8.5 z, 4, Ar), 6.67 (d, J = 8.5 z, 4, Ar), (m, 6, C and C2C), (m, 2, C2C), 2.10 (s, C3C2), (m, 2, C2C(C3)C2), (m, 2, C(C3)C2C3), (m, 2, C(C3)C2C3), 1.10 (d, J = 7.0 z, 6, C(C3)C2C3), 1.00 (t, J = 7.5 z, 6, C(C3)C2C3), 0.72 (d, J = 3.0 z, 6, C3C), 0.71 (d, J = 3.0 z, 6, C3C), 0.25 (s, 18, ). 13 C M (125 Mz, CDCl3, 25 C, as S5

6 (,,S,S,,)-T2 (C3C2)2): δ 177.1, 162.8, 154.0, 142.8, 142.7, 141.8, 141.7, 138.2, 137.8, 132.4, 132.0, 131.9, , , 129.2, 128.7, 128.6, , , 126.8, 126.7, 123.9, 123.5, 122.6, 116.9, 114.0, 104.3, 96.2, 94.3, 87.9, 74.5, 55.7, 35.1, 26.4, 22.3, 22.2, 22.1, 16.8, 11.6, 0.1. MS (ESI): m/z calcd for C Si2 (M ), ; found Scheme S4. Synthesis of amidine template (S,S,S,S,S,S)-T3. (S,S,S,S,S,S)-T3. Copper (I) iodide (3.73 mg, 19.6 µmol) was added to a solution of (S,S)-A- (236 mg, mmol), (S,S)-L (80.0 mg, mmol), and tetrakis(triphenylphosphine)palladium(0) (22.6 mg, 19.6 µmol) in a TF-diisopropylamine mixture (1/1 (v/v), 10 ml) and the mixture was stirred at 75 C for 23 h. After evaporating the solvents, the residue was purified by column chromatography (-Si2, n-hexane/etac = 1/0 to 5/1 (v/v)) to give pure (S,S,S,S,S,S)-T3 (100 mg, 35.2% yield) as a white solid. Mp: C. I (KBr, cm 1 ): 2157 ( C C), 1637 ( C=). 1 M (500 Mz, CDCl3, 25 C, as (S,S,S,S,S,S)-T3 (C3C2)2): δ (br, 4, ), 7.76 (t, J = 7.5 z, 2, Ar), (m, 4, Ar), (m, 20, Ar), (m, 8, Ar), 7.02 (s, 2, Ar), 6.71 (d, J = 8.5 z, 4, Ar), 6.67 (d, J = 8.5 z, 4, Ar), (m, 6, C and C2C), (m, 2, C2C), 2.10 (s, C3C2), (m, 2, C2C(C3)C2), (m, 2, C(C3)C2C3), (m, 2, C(C3)C2C3), 1.10 (d, J = 7.0 z, 6, C(C3)C2C3), 1.00 (t, J = 7.5 z, 6, C(C3)C2C3), 0.72 (d, J = 3.0 z, 6, C3C), 0.71 (d, J = 3.0 z, 6, C3C), 0.26 (s, 18, ). 13 C M (125 Mz, CDCl3, 25 C, as (S,S,S,S,S,S)-T3 (C3C2)2): δ 177.0, 162.8, 154.0, 142.7, 142.6, , , 138.1, 137.8, 132.4, 132.0, 131.9, , , 129.2, 128.7, 128.5, , , , , 123.9, 123.5, 122.5, 116.9, 114.0, 104.3, 96.2, 94.2, 87.9, 74.4, 55.6, 35.1, 26.3, 22.21, 22.15, 21.9, 16.7, 11.6, 0.1. MS (ESI): m/z calcd for C Si2 (M ), ; found General Procedures for otodimerization. A typical experimental procedure is described below. Stock solutions of 1-Me (8.0 mm; solution I) and 1,1,2,2-tetrachloroethane (7.6 mm; solution II) in degassed dry CDCl3 were prepared. Aliquots of solutions I (0.40 µmol, 50 µl) and II S6

7 (0.38 µmol, 50 µl), and dry CDCl3 (700 µl) were added into a Teflon-valved M tube (5-mm (i.d.)) by a syringe. The solution was degassed five times by means of freeze-pump out-thaw (nitrogen) cycles, and then irradiated with light (> 400 nm) at 25 C for 30 min under nitrogen using a cut-off filter. The reaction progress was monitored by 1 M spectroscopy (Figure S1A). In the same say, the photodimerizations of 1 in the presence of the templates T1-T5 as well as the monomeric amidine (A) were performed in degassed dry CDCl3 at 25 C (for A, T3, and T5) and various temperatures (for T1, T2, and T4) and the conversion of 1, the relative yields of four stereoisomers (regio- and diastereoselectivities), and the enantioselectivity (enantiomeric excess (ee)) of two chiral stereoisomers were determined by 1 M spectroscopy and PLC analyses (see below). 4. Isolation of Stereoisomers of 1-Me, ptical esolution, and Structure Determination. The four stereoisomers obtained after photoirradiation (> 400 nm) of 1-Me (8.0 mm) in degassed CDCl3 (Figure S2Aa) were first separated into three fractions (fr.1, fr.2, and fr.3) by PLC fractionation (Figure 3Aa) (PLC conditions: column, two Inert SIL-100A (0.46 (i.d.) 25 cm); eluent, n- hexane/c2cl2/2-propanol (85:14.8:0.2 (v/v/v)); flow rate, 1.0 ml/min; column temperature, 25 C; detection, UV absorption at 254 nm.). The fr.1 was a mixture of two stereoisomers (syn-t- 3-Me and anti--4-me), which were then further separated into two fractions (fr.4 and fr.5) by PLC fractionation (Figure 3Ab) (PLC conditions: column, CSMSIL 5C18-MS-II and 5C18- A-II (0.46 (i.d.) 25 cm); eluent, Me/CCl3 (85:15 (v/v)); flow rate, 1.0 ml/min; column temperature, 25 C; detection, UV absorption at 254 nm.). The 1 M spectra of the isolated four stereoisomers (fr.2, fr.3, fr.4, and fr.5) are shown in Figure S2Ab-e; the structures (chiral or achiral, syn or anti, and then or T) were determined by optical resolution experiments followed by 2D M measurements (see below and main text). Among four stereoisomers, two are chiral and this was unambiguously revealed by chiral PLC analyses of fr.4 and fr.5, which were separated into two peaks due to enantiomers (Figure 3B), indicating that these fractions are unambiguously assigned to be either a syn-t or an anti- photodimer (PLC conditions: column, CIALPAK IB (0.46 (i.d.) 25 cm); gradient eluent for fr.4 (syn-t-3-me), Me/CCl3 (from 95/5 to 80/20 (v/v) for ca. 80 min); eluent for fr.5 (anti- -4-Me), Me/CCl3 (85:15 (v/v)); flow rate, 1.0 ml/min; column temperature, 25 C; detection, UV absorption at 270 nm.). Each enantiomer was then fractionated by chiral PLC to measure the CD spectra (Figure 3C). S7

8 5. otodimerization of 1 in the Presence of Chiral Templates: Isolation of otodimers, Methyl Esterification, and Enantiomeric Excess Determination. A typical experimental procedure is described below. A mixture of 1 (0.50 mm) and (,,,)-T1 (0.25 mm) in degassed CDCl3 (0.80 ml) was irradiated with light (> 400 nm) for 10 min using a cut-off filter at 25 C. The 1 M spectral changes were shown in Figure S9A. After evaporating the solvent, the residue was purified by column chromatography (-Si2, CCl3/Me/Ac = 10/1/0 to 10/1/0.1 (v/v/v)) to afford a mixture of carboxylic acid photodimers and the amidine template ((,,,)- T1). The carboxylic acid photodimers obtained were converted into the corresponding methyl esters by treatment with (trimethylsilyl)diazomethane and the relative yields of four stereoisomers were estimated by 1 M spectroscopy in CDCl3 (Figures 6a and S9B). The chiral methyl esterified photodimers (3-Me and 4-Me) were then fractionated by PLC and their ee values were determined by chiral PLC according to the methods described above (Figure 3). S8

9 6. otodimerization of Monomers in the Absence of Template 6-1. otodimerization of Carboxylic Acid Methyl Ester Monomer (1-Me) (run 1, Table 1) = 1-octynyl hn > 400 nm 31% 38% 16% 15% 1-Me Me CDCl mm 25 C 30 min anti-t-2-me syn-t-3-me anti--4-me syn--5-me (A) c b a,b a e 0 min c f # d 2 min f hn > 400 nm 6 min 10 min 15 min 30 min 20 min f 31% 2-Me 15% Me 16% 38% 4-Me 3-Me (B) Conversion (%) Me Figure S1. (A) Time-dependent 1 M spectral changes of 1-Me (500 Mz, degassed CDCl3, 25 C, 0.50 mm) upon irradiation of light (> 400 nm) at 25 C. # denotes the 13 C satellite peak of the solvent. The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (B) Time-conversion relationships and (C) kinetic plots of the photodimerization of 1-Me (degassed CDCl3, 25 C, 0.50 mm) estimated from the integral ratios of the peaks for a (1-Me) and the internal standard (1,1,2,2-tetrachloroethane) based on the 1 M spectral changes shown in (A). (D) Positive-mode ESI-MS spectrum (C3C/C3 = 1/1 (v/v)) of 1-Me after irradiation of light (> 400 nm) for 30 min in degassed CDCl3. (C) ln(c/c 0 ) Time (min) 40% S9 ln(c/c 0 ) = -kt k = 0.46 x 10-3 (s -1 ) Time (s) (D) Intensity m/z Intensity observed calcd for [C Si 2 a] (photodimer) m/z

10 X X X X X = = 1-octynyl X X X X anti-t-2-me syn-t-3-me anti--4-me syn--5-me Me (A) (a) mixture of four isomers (b) 2-Me (fr.2) aromatic protons of m-terphenyl unit # * # aromatic protons of dimerized anthracene unit f * e d (c) 3-Me (fr.4) (d) 4-Me (fr.5) (e) 5-Me (fr.3) 7.6 (B) (a) 2-Me (fr.2) (b) 3-Me (fr.4) (c) 4-Me (fr.5) (d) 5-Me (fr.3) x doublet 2 x singlet 2 x doublet 2 x singlet 7.4 (C) 2-Me (a) 500 Mz d, J = 11 z (b) 300 Mz 7.3 d, J = 11 z X x doublet 2-Me anti-t e d X J = 11 z (c) gcsy d(e) e(d) 4.56 d(e) e(d) d e f X d d e e X X 2 x singlet 3-Me syn-t 2 x singlet X 5-Me syn- (D) 4-Me (a) 500 Mz d, J = 11 z (b) 300 Mz d, J = 11 z x doublet X 4-Me anti- e d X J = 11 z (c) gcsy d(e) e(d) d(e) e(d) d e Figure S2. (A) Partial 1 M spectra (500 Mz, CDCl3, 25 C) of photodimers obtained after irradiation of light (> 400 nm) of 1-Me (8.0 mm) (a), isolated anti-t-2-me (0.12 mm) (b), syn- T-3-Me (0.09 mm) (c), anti--4-me (0.06 mm) (d), and syn--5-me (0.06 mm) (e). # and denote the peaks for the unreacted 1-Me and the 13 C satellite peaks of the solvent. (B) Partial 1 M spectra (500 Mz, benzene-d6, 25 C) of isolated anti-t-2-me (0.12 mm) (a), syn-t-3- Me (0.09 mm) (b), anti--4-me (0.06 mm) (c), and syn--5-me (0.06 mm) (d). (C,D) Partial 1 M (500 (a) and 300 Mz (b)) and gcsy spectra (c) of isolated 2-Me (0.12 mm) (C) and 4- Me (0.06 mm) (D) in benzene-d6 at 25 C. S10

11 6-2. otodimerization of Carboxylic Acid Monomer (1) (run 2, Table 1) = 1-octynyl hn > 400 nm 7% 7% 15% 71% 1 CDCl mm 25 C 10 min anti-t-2 syn-t-3 anti--4 syn--5 c b (A) a,b a (B) 0 min c e d # f (a) 2-Me 1 min (b) 3-Me hn > 400 nm 10 min 2 min 4 min 7 min (c) 4-Me (d) 5-Me 71% (e) reaction mixture % 7% 7% (C) Conversion (%) % (D) ln(c/c 0 ) ln(c/c 0 ) = -kt k = 1.4 x 10-3 (s -1 ) Time (min) Time (s) Figure S3. (A) Time-dependent 1 M spectral changes of 1 (500 Mz, degassed CDCl3, 25 C, 0.50 mm) upon irradiation of light (> 400 nm) at 25 C. # denotes the 13 C satellite peak of the solvent. (B) Partial 1 M spectra of isolated anti-t-2-me (a), syn-t-3-me (b), anti--4-me (c), syn--5-me (d), and photodimers obtained after irradiation of light (> 400 nm) of 1 for 10 min in degassed CDCl3 at 25 C (e). The carboxylic acid photodimers obtained were converted to the methyl esters before M measurements (see the Supporting Information [SI]). The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (C) Time-conversion relationships and (D) kinetic plots of the photodimerization of 1 (degassed CDCl3, 25 C, 0.50 mm) estimated from the integral ratios of the peaks for a (1) and the internal standard (1,1,2,2-tetrachloroethane) based on the 1 M spectral changes shown in (A). S11

12 = = 1-octynyl 1 selfassociation (1) 2 arrangement (1) 2 T arrangement DFT-optimized structure intermolecular photodimerization hn anti- precursor DFT calculation conformational change of anthracene units syn- precursor anti-t-2 syn-t-3 7% 7% T-dimers hn hn << anti--4 syn--5 15% 71% syn--selective dimerization Figure S4. Possible mechanism for the syn- selective photodimerization of 1 (0.50 mm) upon photoirradiation in degassed CDCl3 at 25 C. The capped-stick drawing of the energy-minimized structure of self-associated (1)2 optimized by the DFT calculations at the B3LYP level and the 6 31G* basis set in Gaussian 09 program (Gaussian, Inc., Pittsburgh, PA) S4 was also depicted. The 1- octynyl chains at the m-terphenyl groups were substituted with hydrogen atoms for simplifying the calculation. The molecular modeling was performed on a Windows 7 PC using the CompassII Force Field as implemented in the Materials Studio package (Version 8.0; Accelrys Inc.). The initial structure, in which the pendant 1-octynyl groups are replaced by hydrogen atoms, was constructed based on the crystal structure of an analogous self-associated monomeric carboxylic acid. S5 The initial model was then fully optimized by the semi-empirical molecular orbital (M) calculation (PM6 method S6 in MPAC2012 S7 ) and further DFT calculation at the B3LYP/6-31G* level using Gaussian 09 software (Gaussian, Inc., Pittsburgh, PA). S4 Computer resource for the DFT calculation was provided by the Information Technology Center of agoya University. S12

13 7. otodimerization of 1 in the Presence of Amidine Templates 7-1. CD and Absorption Spectra of 1 in the Presence of Amidine Templates Figure S5. CD and absorption spectra of (A) (,)-A (0.50 mm), 1 (0.50 mm), and (,)-A 1 (0.50 mm), (B) (,,,)-T1 (0.25 mm), 1 (0.50 mm), and (,,,)-T1 (1)2 (0.25 mm), (C) (,,S,S,,)-T2 (0.25 mm), 1 (0.50 mm), and (,,S,S,,)-T2 (1)2 (0.25 mm), (D) (S,S,S,S,S,S)- T3 (0.25 mm), 1 (0.50 mm), and (S,S,S,S,S,S)-T3 (1)2 (0.25 mm), (E) (,,,,,)-T4 (0.25 mm), 1 (0.50 mm), and (,,,,,)-T4 (1)2 (0.25 mm), and (F) (,,S,S,,)-T5 (0.25 mm), 1 (0.50 mm), and (,,S,S,,)-T5 (1)2 (0.25 mm) in CDCl3 at 25 C. S13

14 Figure S6. Temperature-dependent CD and absorption spectral changes of (A) (,)-A 1 (0.50 mm), (B) (,,,)-T1 (1)2 (0.25 mm), (C) (,,S,S,,)-T2 (1)2 (0.25 mm), and (D) (,,,,,)-T4 (1)2 (0.25 mm) in CDCl3. S14

15 7-2. otodimerization of 1 in the Presence of Monomeric Amidine ((,)-A) (run 3, Table 1) = 1-octynyl (,)-A 1 hn > 400 nm CDCl mm 25 C 30 min 6% ee 5% ee 42% 42% 9% 7% anti-t-2 syn-t-3 anti--4 syn--5 (A) c b a,b e 0 min salt bridge a c d 5 min hn > 400 nm 10 min 15 min 20 min 30 min # Figure S7. (A) Time-dependent 1 M spectral changes of 1 (500 Mz, degassed CDCl3, 25 C, 0.50 mm) in the presence of (,)-A (5.0 mm) upon irradiation of light (> 400 nm) at 25 C. # denotes the peak of hydrochloride salt of (,)-A (ca. 10% after 30 min). (B) Partial 1 M spectra of isolated anti-t-2-me (a), syn-t-3-me (b), anti--4-me (c), syn--5-me (d), and (e) photodimers obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (,)-A (5.0 mm) for 30 min in degassed CDCl3 at 25 C. The carboxylic acid photodimers obtained were isolated and then converted to the methyl esters before M measurements (see SI). The ee value determined by chiral PLC is also shown (see Figure 3B). The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (C) Time-conversion relationships and (D) kinetic plots of the photodimerization of 1 (degassed CDCl3, 25 C, 0.50 mm) in the presence of (,)-A (5.0 mm) estimated from the integral ratios of the peaks for b,c (1) and the internal standard (1,1,2,2-tetrachloroethane) based on the 1 M spectral changes shown in (A). (B) (a) 2-Me (b) 3-Me (c) 4-Me (d) 5-Me (e) reaction mixture % f 42% % 42% (C) Conversion (%) S A 1 50% (D) ln(c/c 0 ) ln(c/c 0 ) = -kt k = 0.40 x 10-3 (s -1 ) Time (min) Time (s)

16 Figure S8. (A) Plausible mechanism for the regioselective photodimerization of 1 in the presence of (,)-A in degassed CDCl3 at 25 C (Figures 5g and S7Be). (B) Possible conformational change of the anthracene unit of 1 complexed with (,)-A, resulting in low enantioselectivity during photodimerization of 1. S16

17 7-3. otodimerization of 1 in the Presence of Dimeric Amidine Template ((,,,)-T1) (run 4, Table 1) = 1-octynyl (,,,)-T1 (1) 2 hn > 400 nm CDCl mm 25 C 10 min 48% ee 16% ee n.d. 73% 22% 5% anti-t-2 syn-t-3 anti--4 syn--5 (A) c b e (B) hn > 400 nm salt bridge 0 min 10 min 2 min 4 min 7 min a,b,c Figure S9. (A) Time-dependent 1 M spectral changes of 1 (500 Mz, degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,,)-T1 (0.25 mm) upon irradiation of light (> 400 nm) at 25 C. (B) Partial 1 M spectra of isolated anti-t-2-me (a), syn-t-3-me (b), anti--4-me (c), syn--5-me (d), and photodimers obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (,,,)-T1 (0.25 mm) for 10 min in degassed CDCl3 at 25 C (e). The carboxylic acid photodimers obtained were isolated and then converted to the methyl esters before M measurements (see SI). The ee values determined by chiral PLC are also shown (see Figure 3B). The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (C) Time-conversion relationships and (D) kinetic plots of the photodimerization of 1 (degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,,)-T1 (0.25 mm) estimated from the integral ratios of the peaks for a,b,c (1) and the internal standard (1,1,2,2-tetrachloroethane) based on the 1 M spectral changes shown in (A). S Conversion (%) a (C) (,,,)-T1 (1) 2 d (D) (a) 2-Me (b) 3-Me (c) 4-Me (d) 5-Me (e) reaction mixture k = 3.4 x (s -1 ) 20 12% Time (min) Time (s) ln(c/c 0 ) % 5% f ln(c/c 0 ) = -kt 73%

18 (A) syn-t si-si photodimerization enantioselectivity () < () re-re photodimerization = 1-octynyl ()-syn-t-3 ()-syn-t-3 (B) anti- enantioselectivity () or () si-si photodimerization (,,,)-T1 72% ee 4% ee re-re photodimerization (,,S,S,,)-T2 ()-anti--4 86% ee 22% ee low temperature high temperature ()-anti--4 Figure S10. Possible mechanism for the enantioselective photodimerization of 1 in the presence of (,,,)-T1 and (,,S,S,,)-T2 regulated by a reversible conformational change of the anthracene units, resulting in the preferential formations of optically-active ()-syn-t-3 (A) and ( )- or ()-anti--4 dimers (B). S18

19 7-4. otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((,,S,S,,)-T2) (run 5, Table 1) = 1-octynyl (,,S,S,,)-T2 (1) 2 hn > 400 nm CDCl mm 25 C 10 min 40% ee 8% ee n.d. 87% 13% n.d. anti-t-2 syn-t-3 anti--4 syn--5 (A) c b e (B) hn > 400 nm 0 min 10 min 2 min 4 min 7 min salt bridge 13.4 a,b,c (C) 100 Conversion (%) a (,,S,S,,)-T2 (1) 2 30% d (D) ln(c/c 0 ) (a) 2-Me (b) 3-Me (c) 4-Me (d) 5-Me (e) reaction mixture 13% f d,e ln(c/c 0 ) = -kt k = 2.1 x 10-3 (s -1 ) 87% Time (min) Time (s) Figure S11. (A) Time-dependent 1 M spectral changes of 1 (500 Mz, degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,S,S,,)-T2 (0.25 mm) upon irradiation of light (> 400 nm) at 25 C. (B) Partial 1 M spectra of isolated anti-t-2-me (a), syn-t-3-me (b), anti--4-me (c), syn--5-me (d), and photodimers obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (,,S,S,,)-T2 (0.25 mm) for 10 min in degassed CDCl3 at 25 C (e). The carboxylic acid photodimers obtained were isolated and then converted to the methyl esters before M measurements (see SI). The ee values determined by chiral PLC are also shown (see Figure 3B). The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (C) Time-conversion relationships and (D) kinetic plots of the photodimerization of 1 (degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,S,S,,)-T2 (0.25 mm) estimated from the integral ratios of the peaks for a,b,c (1) and the internal standard (1,1,2,2- tetrachloroethane) based on the 1 M spectral changes shown in (A). S19

20 7-5. otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((S,S,S,S,S,S)-T3) (run 6, Table 1) = 1-octynyl (S,S,S,S,S,S)-T3 (1) 2 hn > 400 nm CDCl mm 25 C 10 min 28% ee -6% ee n.d. 85% 15% n.d. anti-t-2 syn-t-3 anti--4 syn--5 (A) hn > 400 nm 0 min 1 min 10 min 2 min 4 min 7 min salt bridge 13.4 a,b,c (C) 100 Conversion (%) c b a e (S,S,S,S,S,S)-T3 (1) 2 36% d (D) ln(c/c 0 ) (B) (a) 2-Me (b) 3-Me (c) 4-Me (d) 5-Me (e) reaction mixture 15% f d,e ln(c/c 0 ) = -kt k = 1.7 x 10-3 (s -1 ) 85% Time (min) Time (s) Figure S12. (A) Time-dependent 1 M spectral changes of 1 (500 Mz, degassed CDCl3, 25 C, 0.50 mm) in the presence of (S,S,S,S,S,S)-T3 (0.25 mm) upon irradiation of light (> 400 nm) at 25 C. (B) Partial 1 M spectra of isolated anti-t-2-me (a), syn-t-3-me (b), anti--4-me (c), syn--5-me (d), and photodimers obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (S,S,S,S,S,S)-T3 (0.25 mm) for 10 min in degassed CDCl3 at 25 C (e). The carboxylic acid photodimers obtained were isolated and then converted to the methyl esters before M measurements (see SI). The ee values determined by chiral PLC are also shown (see Figure 3B). The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (C) Time-conversion relationships and (D) kinetic plots of the photodimerization of 1 (degassed CDCl3, 25 C, 0.50 mm) in the presence of (S,S,S,S,S,S)-T3 (0.25 mm) estimated from the integral ratios of the peaks for a,b,c (1) and the internal standard (1,1,2,2-tetrachloroethane) based on the 1 M spectral changes shown in (A). S20

21 7-6. otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((,,,,,)-T4) (run 7, Table 1) = 1-octynyl 14% ee 62% ee (,,,,,)-T4 (1) 2 hn > 400 nm CDCl mm 25 C 10 min 25% 25% 43% 7% anti-t-2 syn-t-3 anti--4 syn--5 (A) 0 min 2 min hn 4 min > 400 nm 6 min 8 min 10 min salt bridge a,b,c c b a Figure S13. (A) Time-dependent 1 M spectral changes of 1 (500 Mz, degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,,,,)-T4 (0.25 mm) upon irradiation of light (> 400 nm) at 25 C. (B) Partial 1 M spectra of isolated anti-t-2-me (a), syn-t-3-me (b), anti--4-me (c), syn--5-me (d), and photodimers obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (,,,,,)-T4 (0.25 mm) for 10 min in degassed CDCl3 at 25 C (e). The carboxylic acid photodimers obtained were isolated and then converted to the methyl esters before M measurements (see SI). The ee values determined by chiral PLC are also shown (see Figure 3B). The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (C) Time-conversion relationships and (D) kinetic plots of the photodimerization of 1 (degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,,,,)-T4 (0.25 mm) estimated from the integral ratios of the peaks for a,b,c (1) and the internal standard (1,1,2,2- tetrachloroethane) based on the 1 M spectral changes shown in (A) (C) 100 Conversion (%) e d (D) (B) (a) 2-Me (b) 3-Me (c) 4-Me (d) 5-Me (e) reaction mixture 20 24% -1.6 k = 2.8 x 10-3 (s -1 ) (,,,,,)-T4 (1) Time (min) Time (s) ln(c/c 0 ) % f % ln(c/c 0 ) = -kt 25% 25% S21

22 7-7. otodimerization of 1 in the Presence of Dimeric Amidine Template with Chiral Linker ((,,S,S,,)-T5) (run 8, Table 1) = 1-octynyl 26% ee 24% ee (,,S,S,,)-T5 (1) 2 hn > 400 nm CDCl mm 25 C 10 min 23% 23% 40% 14% anti-t-2 syn-t-3 anti--4 syn--5 (A) hn > 400 nm 0 min 2 min 4 min 6 min 8 min 10 min salt bridge 13.5 a,b,c c b a (br) (C) 100 Conversion (%) (,,S,S,,)-T5 (1) 2 Figure S14. (A) Time-dependent 1 M spectral changes of 1 (500 Mz, degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,S,S,,)-T5 (0.25 mm) upon irradiation of light (> 400 nm) at 25 C. (B) Partial 1 M spectra of isolated anti-t-2-me (a), syn-t-3-me (b), anti--4-me (c), syn--5-me (d), and photodimers obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (,,S,S,,)-T5 (0.25 mm) for 10 min in degassed CDCl3 at 25 C (e). The carboxylic acid photodimers obtained were isolated and then converted to the methyl esters before M measurements (see SI). The ee values determined by chiral PLC are also shown (see Figure 3B). The relative yields (%) of four stereoisomers were estimated from the integral ratios of the peaks for f. (C) Time-conversion relationships and (D) kinetic plots of the photodimerization of 1 (degassed CDCl3, 25 C, 0.50 mm) in the presence of (,,S,S,,)-T5 (0.25 mm) estimated from the integral ratios of the peaks for a,b,c (1) and the internal standard (1,1,2,2- tetrachloroethane) based on the 1 M spectral changes shown in (A). e d (D) (B) (a) 2-Me (b) 3-Me (c) 4-Me (d) 5-Me (e) reaction mixture k = 3.3 x 10-3 (s -1 ) 14% Time (min) Time (s) ln(c/c 0 ) % f % ln(c/c 0 ) = -kt 23% 23% S22

23 (S,S)-CC (,,S,S,,)-T5 salt bridge formation (S,S)-CC (S,S) (S,S) salt bridge (,,S,S,,)-T5 complementary duplex Figure S15. Capped-stick drawing of the DFT-optimized structure for the complementary duplex formed between carboxylic acid ((S,S)-CC) and amidine ((,,S,S,,)-T5) dimers connected with an (S,S)-1,2-cyclohexanediamine-based bis-amide linker. S8 S23

24 Figure S16. Possible mechanism for the regio- (T or ) and diastereo (syn or anti) selective photodimerization of 1 in the presence of (,,,,,)-T4 regulated by a reversible conformational change of the amidine dimer template and anthracene units of 1, resulting in the formations of anti--4 (A), syn--5 (B), syn-t-3 (C), and anti-t-2 dimers (D). S24

25 Figure S17. Possible mechanism for the enantioselective photodimerization of 1 in the presence of (,,,,,)-T4 regulated by a reversible conformational change of the anthracene units, resulting in the preferential formations of optically-active ()-anti--4 (A) and ()-syn-t-3 dimers (B). S25

26 (A) T1 syn-t-3 anti--4 syn--5 16% 6% (a) 50 C 22% (b) 25 C 5% 29% (c) 0 C 32% (d) 15 C 38% (e) 30 C 54% (f) 50 C 7.18 (B) T1 73% e 71% d f 68% 62% 46% ()-anti--4 (C) T1 ()-syn-t-3 ()-syn-t-3 (a) 50 C (b) 25 C (a) 50 C 50 % ee 48 % ee 48 % ee (c) 0 C (d) 15 C (b) 25 C (c) 0 C (d) 15 C 50 % ee (e) 30 C (f) 50 C f 78% (e) 30 C 44 % ee 30% ee ()-anti--4 4 % ee 16 % ee 32 % ee 40 % ee 54 % ee 72% ee (f) 50 C etention Time (min) etention Time (min) Figure S18. (A) Partial 1 M spectra (500 Mz, CDCl3, 25 C) of photodimers (syn-t-3, anti--4, and syn--5) (af) obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (,,,)-T1 (0.25 mm) in degassed CDCl3 at 50 (a), 25 (b), 0 (c), 15 (d), 30 (e), and 50 C (f) (runs 1-6, Table 2). The syn-t-3 and anti--4 photodimers obtained were isolated and converted to the methyl esters before M measurements (see SI). The peak assignments (af) were performed by comparing the 1 M spectra of the authentic photodimers (Figure 5ad). (B,C) UV detected (270 nm) PLC chromatograms for the resolution of the corresponding methyl esters of the isolated syn-t-3 (B) and anti--4 (C) (see Figure 3B). and denote the signs of the Cotton effect at 340 nm. S26

27 syn-t-3 (A) T4 anti--4 syn--5 2 (a) 50 C T anti-t-2 f 3 4 e 5 27% 21% 40% 12% (b) 25 C 25% 25% 43% 7% (c) 0 C 27% 22% 46% 5% (d) 15 C 23% 20% 49% 8% (e) 30 C 22% 20% 54% 4% (f) 50 C 17% 17% 60% 6% (B) T4 ()-anti--4 (C) T4 ()-anti--4 ()-syn-t-3 ()-syn-t-3 (a) 50 C (b) 25 C (c) 0 C (d) 15 C (e) 30 C (f) 50 C (a) 50 C 8 % ee (b) 25 C 14 % ee (c) 0 C 14 % ee (d) 15 C 20 % ee 20 % ee 22% ee d f (e) 30 C (f) 50 C 54 % ee 62% ee 70 % ee 78 % ee 84 % ee 88% ee etention Time (min) etention Time (min) Figure S19. (A) Partial 1 M spectra (500 Mz, CDCl3, 25 C) of photodimers (af) obtained after irradiation of light (> 400 nm) of 1 (0.50 mm) in the presence of (,,,,,)-T4 (0.25 mm) in degassed CDCl3 at 50 (a), 25 (b), 0 (c), 15 (d), 30 (e), and 50 C (f) (runs 14-19, Table 2). The carboxylic acid photodimers obtained were isolated and converted to the methyl esters before M measurements (see SI). The peak assignments (af) were performed by comparing the 1 M spectra of the authentic photodimers (Figure 5ad). (B,C) UV detected (270 nm) PLC chromatograms for the resolution of the corresponding methyl esters of the isolated syn-t-3 (B) and anti--4 (C) (see Figure 3B). and denote the signs of the Cotton effect at 340 nm. S27

28 ()-syn-t-3 ()-syn-t-3 template-directed photodimerization (,,S,S,,)-T2 (1) 2 zigzag shape > 50 C or low concentration ([T2 (1) 2 ] = mm) 50 C aggregation conformational change of template 50 C no aggregation crescent shape temperature-independent template-directed photodimerization 50 ~ 50 C anti--4 Figure S20. Plausible mechanism for the concentration-dependent inversion of the enantioselectivity during the photodimerization of 1 in the presence of (,,S,S,,)-T2 at 50 C induced by self-assembled supramolecular aggregates formation of (,,S,S,,)-T2 (1)2, thus producing the syn-t-3 dimer with the opposite configuration (bottom). S28

29 8. Spectroscopic Data = 1-octynyl 1 Figure S21. 1 M spectrum of 1 in CDCl3 at 25 ºC. = 1-octynyl 1 Figure S C M spectrum of 1 in CDCl3 at 25 ºC. S29

30 = 1-octynyl Me 1-Me Figure S23. 1 M spectrum of 1-Me in CDCl3 at 25 ºC. = 1-octynyl Me 1-Me Figure S C M spectrum of 1-Me in CDCl3 at 25 ºC. S30

31 (,,S,S,,)-T2 Figure S25. 1 M spectrum of (,,S,S,,)-T2 (C3C2)2 in CDCl3 at 25 ºC. (,,S,S,,)-T2 Figure S C M spectrum of (,,S,S,,)-T2 (C3C2)2 in CDCl3 at 25 ºC. S31

32 (S,S,S,S,S,S)-T3 Figure S27. 1 M spectrum of (S,S,S,S,S,S)-T3 (C3C2)2 in CDCl3 at 25 ºC. (S,S,S,S,S,S)-T3 Figure S C M spectrum of (S,S,S,S,S,S)-T3 (C3C2)2 in CDCl3 at 25 ºC. S32

33 Me anti-t-2-me d e f = 1-octynyl Me f # CMe x Figure S29. 1 M spectrum of anti-t-2-me in CDCl3 at 25 ºC. # and x denote the 13 C satellite peak of the solvent and the peak of 1,1,2,2-tetrachloroethane used as an internal standard, respectively. e = 1-octynyl Me d f syn-t-3-me Me # f CMe x Figure S30. 1 M spectrum of syn-t-3-me in CDCl3 at 25 ºC. # and x denote the 13 C satellite peak of the solvent and the peak of 1,1,2,2-tetrachloroethane used as an internal standard, respectively. S33

34 = 1-octynyl d e f Me anti--4-me Me # f x CMe Figure S31. 1 M spectrum of anti--4-me in CDCl3 at 25 ºC. # and x denote the 13 C satellite peak of the solvent and the peak of 1,1,2,2-tetrachloroethane used as an internal standard, respectively. e Me = 1-octynyl d f syn--5-me Me # f x CMe Figure S32. 1 M spectrum of syn--5-me in CDCl3 at 25 ºC. # and x denote the 13 C satellite peak of the solvent and the peak of 1,1,2,2-tetrachloroethane used as an internal standard, respectively. S34

35 (A) anti-t-2-me Intensity observed m/z (B) syn-t-3-me m/z Intensity observed m/z (C) anti--4-me m/z Intensity observed m/z (D) syn--5-me m/z Intensity observed m/z m/z calcd for [C Si 2 a] (photodimer) Figure S33. Positive-mode ESI-MS spectra (C3C) of anti-t-2-me (A), syn-t-3-me (B), anti--4-me (C), and syn--5-me (D) m/z S35

36 9. Supporting eferences S1 Maeda, T.; Furusho, Y.; Sakurai, S.-i.; Kumaki, J.; koshi, K.; Yashima, E. J. Am. Chem. Soc. 2008, 130, S2 Tanaka, Y.; Katagiri,.; Furusho, Y.; Yashima, E. Angew. Chem., Int. Ed. 2005, 44, S3 Yamada,.; Furusho, Y.; Yashima, E. J. Am. Chem. Soc. 2012, 134, S4 Gaussian 09, evision D.01, Frisch, M. J.; Trucks, G. W.; Schlegel,. B.; Scuseria, G. E.; obb, M. A.; Cheeseman, J..; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; akatsuji,.; Caricato, M.; Li, X.; ratchian,. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; ada, M.; Ehara, M.; Toyota, K.; Fukuda,.; asegawa, J.; Ishida, M.; akajima, T.; onda, Y.; Kitao,.; akai,.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; gliaro, F.; Bearpark, M.; eyd, J. J.; Brothers, E.; Kudin, K..; Staroverov, V..; Kobayashi,.; ormand, J.; aghavachari, K.; endell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; ega,.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts,.; Stratmann,. E.; Yazyev,.; Austin, A. J.; Cammi,.; Pomelli, C.; chterski, J. W.; Martin,. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; rtiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, S5 Makiguchi, W.; Kobayashi, S.; Furusho, Y.; Yashima, E. Angew. Chem., Int. Ed. 2013, 52, S6 Stewart, J. J. P. J. Mol. Model. 2007, 13, S7 Stewart, J. J. P. MPAC2012, Stewart Computational Chemistry, Colorado Springs, C, USA, (2012). S8 Makiguchi, W.; Tanabe, J.; Yamada,.; Iida,.; Taura, D.; usaka,.; Yashima, E. at. Commun. 2015, 6, 7236; DI: /ncomms8236. S36