supporting online material for...2010/04/26 · spectra were measured on a bruker maxis®. the data...

www.sciencemag.org/cgi/content/full/science.1188605/DC1

Supporting Online Material for

Self-Assembled M24L48 Polyhedra and Their Sharp Structural Switch

upon Subtle Ligand Variation

Qing-Fu Sun, Junji Iwasa, Daichi Ogawa, Yoshitaka Ishido, Sota Sato, Tomoji Ozeki, Yoshihisa Sei, Kentaro Yamaguchi, Makoto Fujita*

*To whom correspondence should be addressed. E-mail: [email protected]

Published 29 April 2010 on Science Express

DOI: 10.1126/science.1188605

This PDF file includes:

Materials and Methods Figs. S1 to S31 Tables S1 to S4 References

S1

Contents

General

Procedure

• Synthesis and physical properties of ligands 1

• Synthesis and physical properties of sphere 2

• General procedure for synthesis of mixed-ligand spheres

• Synchrotron single crystal X-ray diffraction study

Figures and Tables

• Figs. S1 to S19: NMR spectra of sphere 2

• Figs. S20 to S28: CSI-TOF mass spectra of sphere 2

• Tables S1 to S3: Selected mass information

• Fig. S29: 1H DOSY spectra of mixed-ligand spheres

• Fig. S30: CSI-TOF mass spectra of mixed-ligand spheres

• Table S4: Crystal data and refinement of 2c

• Fig. S31: Ortep drawing

References for Supporting Materials

S2

1. General

NMR spectra were measured on a Bruker DRX-500 (500 MHz) spectrometer equipped

with a BBO gradient probe, a Bruker AV-500 (500 MHz) spectrometer equipped with a TCI

gradient CryoProbe, a JEOL ECA-600 (600 MHz) spectrometer equipped with a gradient

cold probe (53040HCNVC), and Bruker AV-700 (700 MHz) spectrometer equipped with a

TCI gradient CryoProbe. IR spectra were measured as KBr pellets using a DIGILAB

Scimitar FTS-2000 instrument. Melting points were determined on a Yanaco MP-500V

apparatus. Elemental analyses were performed on a Yanaco MT-6. GC mass spectra were

measured on an Agilent Technologies 5973N spectrometer with an EI ionization source

equipped with an Agilent Technologies 6890N gass chromatography system. MALDI-TOF

mass spectra were measured on an Applied Boisystem Voyager DE-STR. CSI-TOF mass

spectra were measured on a Bruker maXis®. The data analyses of CSI-TOF mass spectra

were processed on a Bruker DataAnalysis (Version 4.0 SP 2) software and the simulations

were performed on a Bruker IsotopePattern software.

Solvents and reagents were purchased from TCI Co., Ltd., WAKO Pure Chemical Industries

Ltd., and Sigma-Aldrich Co. All the chemicals were of reagent grade and used without any

further purification.

S3

2. Procedure

3-Bromo-2,5-diiodothiophene was synthesized in the same method as for 3-bromo-4-

methyl-2,5-diiodothiophene (S1) in 89% yield. 1H NMR (CDCl3, 500 MHz, 300 K) 7.02 (s,

1H); GC-MS m/z calcd for C4HBrI2S ([M]+) 413.7, found 413.7. 2,5-Dibromo-3,4-

ethylenedioxythiophene (S2) was synthesized according to the reported procedure.

Synthesis and physical properties of ligands 1a-c

S NN

NBO

O

Pd(PPh3)4 (0.1 eq.)

K3PO4 (8.0 eq.)

1,4-dioxane

1a-c

R'R

SX X

R'R

a: X = Br; R = R' = Hb: X = I; R = H, R' = Brc: X = Br; R, R' = –OCH2CH2O–

(2.8 eq.)

90 °C5a-c

Scheme S1. Synthesis of ligand 1.

Synthesis of 2,5-dipyridylthiophene (1a): 4-Pyridylboronic acid pinacol ester (2.01 g, 9.80

mmol), tetrakis(triphenylphosphine) palladium(0) (407 mg, 0.352 mmol), potassium

phosphate (5.95 g, 28.0 mmol) were added into a 250 mL two-necked flask. Under argon

atmosphere, 1,4-dioxane (70 mL) and 2,5-dibromothiophene 5a (394 L, d = 2.15 mg/mL,

847 mg, 3.61 mmol) were added successively, and the suspension was stirred for 72 h at 90

°C. After cooling down to room temperature, the residue was filtered and washed with

chloroform. The filtrate was evaporated to give a dark brown residue, which was further

purified by silica gel column chromatography eluted with a mixture of chloroform and

methanol (200:1 in volume) to give the ligand 1a as a light yellow solid (575 mg, 2.49 mmol)

in 69% yield. m.p. 174-175 °C. GC-MS m/z calcd for C14H10N2S ([M]+) 238.1, found 238.1.

1H NMR (500 MHz, DMSO-d6, 300 K) 8.62 (d, J = 6.0 Hz, 4H), 7.92 (s, 2H), 7.71 (d, J =

6.0 Hz, 4H). 13C NMR (125 MHz, DMSO-d6, 300 K) 150.4 (CH), 141.7 (C), 139.8 (C),

128.0 (CH), 119.4 (CH). IR (KBr, cm–1) 3060, 3032, 1596, 1543, 1487, 1452, 1414, 1288,

1219, 991, 956, 861, 813, 687, 575, 476, 425. Elemental Analysis Calcd for C14H10N2S: C,

70.56%; H, 4.23%; N, 11.76%. Found: C, 70.72%; H, 4.50%; N, 11.51%.

S4

Synthesis of 3-bromo-2,5-dipyridylthiophene (1b): According to the same procedure for

1a, the ligand 1b was synthesized from 3-bromo-2,5-diiodothiophene 5b as a light yellow

solid in 39% yield. m.p. 160-161 °C. GC-MS m/z calcd for C14H9BrN2S ([M]+) 238.1, found

238.1. 1H NMR (500 MHz, DMSO-d6, 300 K) 8.71 (d, J = 6.3 Hz, 2H), 8.64 (d, J = 6.3 Hz,

2H), 8.05 (s, 1H), 7.74-7.72 (m, 4H). 13C NMR (125 MHz, DMSO-d6, 300 K) 150.5 (CH),

150.3 (CH), 141.2 (C), 139,0 (C), 138.6 (C), 135.5 (C), 130.9 (CH), 122.4 (CH), 119.3 (CH),

110.2 (C). IR (KBr, cm–1) 3086, 3029, 1589, 1541, 1481, 1445, 1414, 1347, 1317, 1223, 993,

962, 839, 817, 694, 620, 577, 529, 495, 451. Elemental Analysis Calcd for C14H9BrN2S: C,

53.01%; H, 2.86%; N, 8.83%. Found: C, 52.86%; H, 3.00%, N, 8.54%.

Synthesis of 2,5-dipyridyl-3,4,-ethylenedioxylthiophene (1c): According to the same

procedure for 1a, the ligand 1c was synthesized from 2,5-dibromo-3,4-

ethylenedioxythiophene 5c as a light yellow solid in 89% yield. m.p. 256-257 °C. MALDI-

TOF-MS (matrix: 9-nitroanthracene) m/z Calcd for C16H12N2O2S ([M+H]+) 297.1, found

297.1. 1H NMR (500 MHz, CDCl3, 300 K) 8.59 (d, J = 6 Hz, 4H), 7.63 (d, J = 6 Hz, 4H),

4.44 (s, 4H). 13C NMR (125 MHz, CDCl3, 300 K) 150.3 (CH), 141.4 (C), 139,7 (C), 120.0

(CH), 115.0 (C), 64.8 (CH2). IR (KBr, cm–1) 3024, 2944, 1594, 1543, 1516, 1490, 1476,

1447, 1411, 1373, 1325, 1298, 1218, 1107, 1074, 1027, 992, 938, 915, 852, 813, 795, 649,

596, 489, 468. Elemental Analysis Calcd for C16H12N2O2S•0.3H2O: C, 63.69%; H, 4.21%; N,

9.28%. Found: C, 63.61%5; H, 4.12%; N, 8.96%.

Synthesis and physical properties of sphere 2a-c

S NN

R'R

S NN

R'R

24 Pd(II)

Pd Pd48

a: R = R' = H; b: R = H, R' = Br; c: R, R' = –OCH2CH2O–

1a-c 2a-c

Scheme S2. Synthesis of sphere 2.

S5

Synthesis of sphere 2a (NO3– salt): Ligand 1a (18.2 mg, 76.4 μmol) was treated with

Pd(NO3)2 (8.80 mg, 38.2 μmol) in DMSO (3.81 mL) at 70 °C for 17 h. 1H NMR confirmed

the quantitative formation of 2a. An excess amount of a mixture of ethyl acetate and diethyl

ether (1:1 in volume) was added to the solution of sphere 2a, and the precipitate was

collected by filtration and dried in vacuo to give sphere 2a as a yellow solid (20.1 mg, 75%

isolated yield). m.p. > 300 °C (decomposed). 1H NMR (500 MHz, DMSO-d6, 300 K) 9.25

(br, 192H), 8.00 (br, 288H). Diffusion coefficient (DMSO-d6, 300 K): D = 3.3 10–11 m2•S-1.

13C NMR (176 MHz, DMSO-d6, 300 K) 152.5 (CH), 142.5 (C + C), 132.2 (CH), 123.4

(CH). The 13C NMR spectrum was difficult to measure due to the severe broadness of the

signals in DMSO-d6, and we finally obtained the spectrum after 320,000 times of acquisitions

on 700 MHz NMR system equipped with TCI cryoprobe. IR (KBr, cm–1) 3441, 1728, 1610,

1546, 1489, 1431, 1381, 1358, 1327, 1287, 1220, 1069, 1037, 992, 810, 716, 575, 477.

Elemental Analysis Calcd for C672H480N144O144S48Pd24•75DMSO: C, 43.25%; H, 4.11%; N,

8.83%. Found: C, 42.91%5; H, 3.97%; N, 8.83%. DMSO was found very difficult to be

completely removed, and the residual DMSO was confirmed by 1H NMR ( 2.62 ppm,

singlet, in CDCl3) by sonicating the suspension of sphere 2a in CDCl3 over 1 h.

Synthesis of sphere 2a (BF4– salt): Complexation proceeded in acetonitrile using Pd(BF4)2.

1H NMR (500 MHz, CD3CN, 300 K) 8.95 (br, 192H), 7.62 (br, 288H). 13C NMR (125

MHz, CD3CN, 300 K) 152.4 (CH), 144.9 (C), 142.9 (C), 131.6 (CH), 123.7 (CH). The

signals in 13C NMR is narrower than those in dimethyl sulfoxide-d6 using Pd(NO3)2, and 1H-

{13C} HSQC NMR spectrum was also measured. CSI-TOF-MS (BF4– salt, CH3CN): The

following picked signals are those of monoisotropic ion signals (S3). m/z Calcd for [M –

16(BF4–)]16+ 1048.5333, found 1048.5862; Calcd for [M – 17(BF4

–)]17+ 981.7370, found

981.7276; Calcd for [M – 18(BF4–)]18+ 922.3625, found 922.3525; Calcd for [M – 19(BF4

–

)]19+ 869.2379, found 869.2290; Calcd for [M – 20(BF4–)]20+ 821.4258, found 821.4162;

Calcd for [M – 21(BF4–)]21+ 778.1673, found 778.1580; Calcd for [M – 22(BF4

–)]22+

738.8413, found 738.8292; Calcd for [M – 23(BF4–)]23+ 702.9350, found 702.9241; Calcd for

[M – 24(BF4–)]24+ 670.0208, found 670.0139.

Synthesis of sphere 2b (NO3– salt): Ligand 1b (33.94 mg, 107.0 μmol) was treated with

Pd(NO3)2 (12.35 mg, 53.60 μmol) in dimethyl sulfoxide (5.35 mL) at 70 °C for 2 h. 1H NMR

S6

confirmed the quantitative formation of 2b. An excess amount of a mixture of ethyl acetate

and diethyl ether (1:1 in volume) was added to the solution of sphere 2b, the precipitate was

collected by filtration and dried in vacuo to give sphere 2b as yellow solid (39.21 mg, 85%

isolated yield). m.p. > 265 °C (decomposed). 1H NMR (500 MHz, DMSO–d6, 300 K) 9.27

(br, 192H), 8.09 (br, 240H). Diffusion coefficient (DMSO–d6, 300 K): D = 3.3 10–11 m2•S–

1. IR (KBr, cm–1) 3393, 3089, 1726, 1609, 1486, 1427, 1381, 1317, 1269, 1219, 1068, 1040,

995, 825, 721, 619, 578, 540, 501, 473. Elemental Analysis Calcd for

C672H432N144O144Br48S48Pd24•68DMSO: C, 37.23%; H, 3.25%; N, 7.74%. Found: C, 36.90%;

H, 2.88%; N, 7.44%.

Synthesis of sphere 2b (BF4– salt): Complexation proceeded in acetonitrile using Pd(BF4)2.

1H NMR (500 MHz, CD3CN, 300 K) 8.99 (br, 192H), 7.82 (br, 240H). We tried 13C NMR

measurement but failed, presumably because of the severe broadness of the signals. CSI-

TOF-MS (BF4– salt, CH3CN): The following picked signals are those at highest intensities,

because the monoisotropic ion signals placed at low intense region in the isotope patterns.

m/z Calcd for [M – 15(BF4–)]15+ 1376.7461, found 1376.7537; Calcd for [M – 16(BF4

–)]16+

1284.7619, found 1284.7655; Calcd for [M – 17(BF4–)]17+ 1204.1874, found 1204.1910;


–)]19+

1068.2725, found 1068.2758; Calcd for [M – 20(BF4–)]20+ 1010.5587, found 1010.5622;


–)]22+

910.7802, found 910.7837; Calcd for [M – 23(BF4–)]23+ 867.3983, found 867.4016; Calcd for

[M – 24(BF4–)]24+ 827.4649, found 827.4679; Calcd for [M – 25(BF4

–)]25+ 791.0461, found


–

)]27+ 726.1534, found 726.1581; Calcd for [M – 28(BF4–)]28+ 696.8979, found 696.9046.

Synthesis of sphere 2c (NO3– salt): Ligand 1c (20.96 mg, 70.73 μmol) was treated with

Pd(NO3)2 (8.16 mg, 35.41 μmol) in dimethyl sulfoxide (3.57 mL) at 70 °C for 3 h. 1H NMR

confirmed the quantitative formation of 2c. An excess amount of a mixture of ethyl acetate

and diethyl ether (1:1 in volume) was added to the solution of 2c, and the precipitate was

collected by filtration and dried in vacuo to give sphere 2c as yellow solid (23.3 mg, 80%

isolated yield). m.p. > 280 °C (decomposed). 1H NMR (500 MHz, DMSO-d6, 300 K) 9.22

(br, 96H), 9.13 (br, 96H), 7.90 (br, 96H), 7.79 (br, 96H), 4.42 (br, 192H). Diffusion

S7

coefficient (DMSO-d6, 300 K): D = 3.3 10–11 m2•S–1. IR (KBr, cm–1) 3468, 3359, 3067,

2364, 1730, 1606, 1576, 1541, 1495, 1481, 1447, 1429, 1364, 1327, 1302, 1270, 1219, 1142,

1121, 1070, 1037, 977, 936, 913, 852, 828, 798, 734, 677, 596, 545, 498, 446. Elemental

Analysis Calcd for C768H576N144O240S48Pd24•72DMSO: C, 43.16%; H, 4.00%; N, 7.95%.

Found: C, 43.16%5; H, 3.68%; N, 7.99%.

Synthesis of sphere 2c (BF4– salt): Complexation proceeded in acetonitrile using Pd(BF4)2.

1H NMR (500 MHz, CD3CN, 300 K) 8.93 (br, 96H), 8.83 (br, 96H), 7.93 (br, 96H), 7.83

(br, 96H), 4.40 (br, 96H), 4.37 (br, 96H). 13C NMR (150 MHz, CD3CN, 300 K) 151.0

(CH), 144.4 (C), 143.0 (C), 122.4 (CH), 114.2 (C), 65.2 (CH2). 1H-{13C} HSQC and 1H-

{13C} HMBC NMR spectra were also measured. CSI-TOF-MS (BF4– salt, CH3CN): m/z

Calcd for [M – 11(BF4–)]11+ 1817.8020, found 1817.8063; [M – 12(BF4

–)]12+ 1659.0682,

found 1659.0625; Calcd for [M – 13(BF4–)]13+ 1524.7549, found 1524.7441; Calcd for [M –


–)]15+ 1309.8537, found

1309.8450; Calcd for [M – 16(BF4–)]16+ 1222.5501, found 1222.5414; Calcd for [M –


–)]18+ 1077.0441, found

1077.0357; Calcd for [M – 19(BF4–)]19+ 1015.7784, found 1015.7701; Calcd for [M –


–)]21+ 910.7515, found


–

)]23+ 823.9901, found 823.9822; Calcd for [M – 24(BF4–)]24+ 786.0320, found 786.0230;


–)]26+

718.8754, found 718.8538; Calcd for [M – 27(BF4–)]27+ 689.0280, found 689.0395.

Synthesis of sphere 2c (PF6– salt): Complexation proceeded in a mixture of acetonitrile and

dimethyl sulfoxide (1:1 in volume) using Pd(PF6)2. 1H NMR (500 MHz, CD3CN:DMSO-d6 =

1:1, 300 K) 9.26 (br, 96H), 9.16 (br, 96H), 7.88 (br, 96H), 7.77 (br, 96H), 4.42 (br, 96H),

4.37 (br, 96H).

S8

General procedure for synthesis of mixed-ligand spheres

Ligand 1c (0.0900 n mg, 0.300 n mol) and Ligand 3 (0.0667 (10 – n) mg, 0.300

(10 – n) mol) were mixed in dimethyl sulfoxide (0.600 mL), where n = 1,2, ... , 10. The 1c:3

= n:(10 – n) ratio mixture solution was treated with Pd(OTf)2 (1.65 mol) in dimethyl

sulfoxide (0.15 mL) at 70 ºC for 3 h. The quantitative formation of the complexes was

confirmed by 1H NMR. The structures of products were determined by 1H DOSY NMR and

CSI-TOF-MS.

Synchrotron single crystal X-ray diffraction study

The preliminary synchrotron X-ray diffraction studies were carried out at the NW2A

beamline in the PF-AR with the approval of the High Energy Accelerator Research

Organization (KEK) with a diffractometer equipped with a Rigaku 3052P311 CCD detector.

The final synchrotron X-ray diffraction studies were carried out at the BL38B1 beamline in

SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI)

with a diffractometer equipped with an ADSC Quantum210 CCD detector. The collected

diffraction data were processed with the HKL2000 software program. The structure was

solved by direct method using the SHELXS-97 (Sheldrick, 1990) program, and the structural

refinement was performed using the SHELXL-97 (Sheldrick, 1997) program.

Only 6 palladium and 12 sulfur atoms were refined anisotropically, the other 241 non-

hydrogen atoms present in the asymmetrical unit isotropically. CCDC-765717 contains the

supplementary crystallographic data for this paper. These data can be obtained free of charge

via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data

Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44) 1223-336-033; or

[email protected]).

S9

NMR and mass spectra

Fig. S1. 1H NMR spectrum of sphere 2a (NO3– salt) (500 MHz, DMSO-d6, 300 K).

Fig. S2. 13C NMR spectrum of sphere 2a (NO3– salt) (700 MHz, DMSO-d6, 300 K).

S10

Fig. S3. 1H NMR spectrum of sphere 2a (BF4– salt) (500 MHz, CD3CN, 300 K).

Fig. S4. 13C NMR spectrum of sphere 2a (BF4– salt) (125 MHz, CD3CN, 300 K).

S11

Fig. S5. COSY spectrum of sphere 2a (BF4– salt) (500 MHz, CD3CN, 300 K).

Fig. S6. 1H-{13C} HSQC spectrum of sphere 2a (BF4– salt) (500 MHz, CD3CN, 300 K).

S12

Fig. S7. 1H NMR spectrum of sphere 2b (NO3– salt) (500 MHz, DMSO-d6, 300 K).

Fig. S8. 1H NMR spectrum of sphere 2b (BF4– salt) (500 MHz, CD3CN, 300 K).

S13

Fig. S9. COSY spectrum of sphere 2b (BF4– salt) (500 MHz, CD3CN, 300 K).

Fig. S10. 1H NMR spectrum of sphere 2c (NO3– salt) (500 MHz, DMSO-d6, 300 K). There

are two ligands in different chemical environments in the rhombicuboctahedron framework

as indicated in yellow and blue, resulting two pairs of signals.

S14

Fig. S11. 1H NMR spectrum of sphere 2c (BF4– salt) (500 MHz, CD3CN, 300 K).

Fig. S12. 1H NMR spectrum of sphere 2c (PF6– salt) (500 MHz, CD3CN:DMSO-d6 = 1:1,

S15

300 K).

Fig. S13. 13C NMR spectrum of sphere 2c (BF4– salt) (150 MHz, CD3CN, 300 K).

Fig. S14. COSY spectrum of sphere 2c (BF4– salt) (500 MHz, CD3CN, 300 K).

S16

Fig. S15. 1H-{13C} HSQC spectrum of sphere 2c (BF4– salt) (600 MHz, CD3CN, 300 K).

Fig. S16. 1H-{13C} HMBC spectrum of sphere 2c (BF4– salt) (600 MHz, CD3CN, 300 K).

S17

Fig. S17. 1H DOSY spectrum of sphere 2a (NO3– salt) (500 MHz, DMSO-d6, 300 K).

Fig. S18. 1H DOSY spectrum of sphere 2b (NO3– salt) (500 MHz, DMSO-d6, 300 K).

S18

Fig. S19. 1H DOSY spectrum of sphere 2c (NO3– salt) (500 MHz, DMSO-d6, 300 K).

Fig. S20. CSI-TOF mass spectrum of sphere 2a (BF4– salt)

S19

Selected mass information in the 17+ peak

Observed ion

(m/z) Intensity Resolution FWHM

Theoretical mass

Difference (obs.–theo.)

Error (ppm)

980.9627 1043 37165 0.0264 980.9724 –0.0097 –9.9

981.0213 1143 37225 0.0264 981.0312 –0.0099 –10.1

981.0796 1194 38319 0.0256 981.0900 –0.0104 –10.6

981.1387 1210 36487 0.0269 981.1488 –0.0101 –10.3

981.1981 1269 36042 0.0272 981.2077 –0.0096 –9.8

981.2575 1322 38380 0.0256 981.2665 –0.0090 –9.2

981.3154 1300 37929 0.0259 981.3253 –0.0099 –10.1

981.3745 1325 35737 0.0275 981.3841 –0.0096 –9.8

981.4332 1316 38719 0.0254 981.4429 –0.0097 –9.9

981.4911 1306 36429 0.0269 981.5017 –0.0106 –10.8

981.5517 1193 35618 0.0276 981.5606 –0.0089 –9.1

981.6103 1286 37575 0.0261 981.6194 –0.0091 –9.3

981.6680 1158 37655 0.0261 981.6782 –0.0102 –10.4

981.7276 1187 37465 0.0262 981.7370 –0.0094 –9.6

981.7862 1164 37786 0.0260 981.7958 –0.0096 –9.8

981.8445 1088 38956 0.0252 981.8547 –0.0102 –10.4


Observed ion


Theoretical mass


Error (ppm)

921.6304 858 37325 0.0247 921.6404 –0.0100 –10.9

921.6864 885 39326 0.0234 921.6959 –0.0095 –10.3

921.7410 940 36973 0.0249 921.7515 –0.0105 –11.4

921.7966 947 36858 0.0250 921.8070 –0.0104 –11.3

921.8518 1024 38443 0.0240 921.8626 –0.0108 –11.7

921.9080 1070 37385 0.0247 921.9181 –0.0101 –11.0

921.9628 1048 38950 0.0237 921.9737 –0.0109 –11.8

922.0188 994 36332 0.0254 922.0292 –0.0104 –11.3

922.0741 1049 37470 0.0246 922.0848 –0.0107 –11.6

922.1297 1026 37062 0.0249 922.1403 –0.0106 –11.5

922.1851 975 36993 0.0249 922.1959 –0.0108 –11.7

922.2409 977 37204 0.0248 922.2514 –0.0105 –11.4

922.2974 976 36886 0.0250 922.3070 –0.0096 –10.4

922.3525 912 37488 0.0246 922.3625 –0.0100 –10.8

922.4081 899 37431 0.0246 922.4181 –0.0100 –10.8

922.4630 798 34842 0.0265 922.4736 –0.0106 –11.5

Table S1. Selected mass information in 17+ and 18+ peaks of 2a (BF4– salt)

S20

Fig. S21. Observed and simulated (resolving power at 27261) isotope patterns of 17+ peak of

2a (BF4– salt)


2a (BF4– salt)

S21

Fig. S23. CSI–TOF mass spectrum of sphere 2b (BF4– salt).

S22


Observed ion


Theoretical mass


Error (ppm)

1203.7207 86043 46998 0.0256 1203.7170 0.0037 3.1

1203.7795 90834 47749 0.0252 1203.7758 0.0037 3.1

1203.8384 93967 47887 0.0251 1203.8346 0.0038 3.2

1203.8967 95379 46575 0.0259 1203.8934 0.0033 2.7

1203.9558 97932 46754 0.0258 1203.9522 0.0036 3.0

1204.0142 99292 45617 0.0264 1204.0110 0.0032 2.7

1204.0731 101754 47003 0.0256 1204.0698 0.0033 2.7

1204.1320 101797 46316 0.0260 1204.1286 0.0034 2.8

1204.1910 104411 48747 0.0247 1204.1874 0.0036 3.0

1204.2493 102262 46535 0.0259 1204.2462 0.0031 2.6

1204.3085 101231 47871 0.0252 1204.3050 0.0035 2.9

1204.3671 99558 46767 0.0258 1204.3638 0.0033 2.7

1204.4262 98220 47141 0.0256 1204.4226 0.0036 3.0

1204.4848 95437 46323 0.0260 1204.4814 0.0034 2.8

1204.5443 94020 49214 0.0245 1204.5402 0.0041 3.4

1204.6029 89528 47344 0.0254 1204.5990 0.0039 3.2


Observed ion


Theoretical mass


Error (ppm)

1132.0140 88627 45378 0.0250 1132.0103 0.0037 3.3

1132.0693 97338 49107 0.0231 1132.0658 0.0035 3.1

1132.1248 100982 47801 0.0237 1132.1213 0.0035 3.1

1132.1808 104116 47917 0.0236 1132.1769 0.0039 3.4

1132.2357 107370 48366 0.0234 1132.2324 0.0033 2.9

1132.2912 108000 46585 0.0243 1132.2879 0.0033 2.9

1132.3467 108456 46684 0.0243 1132.3435 0.0032 2.8

1132.4025 108229 46930 0.0241 1132.3990 0.0035 3.1

1132.4578 105282 45514 0.0249 1132.4545 0.0033 2.9

1132.5137 104488 45412 0.0249 1132.5101 0.0036 3.2

1132.5693 106021 47154 0.0240 1132.5656 0.0037 3.3

1132.6248 105435 46264 0.0245 1132.6211 0.0037 3.3

1132.6799 103946 45515 0.0249 1132.6767 0.0032 2.8

1132.7352 100094 45241 0.0250 1132.7322 0.0030 2.6

1132.7906 97148 45425 0.0249 1132.7877 0.0029 2.6

1132.8462 91183 44472 0.0255 1132.8433 0.0029 2.6

Table S2. Selected mass information in 17+ and 18+ peaks of 2b (BF4– salt).

S23


2b (BF4– salt).


2b (BF4– salt).

S24

Fig. S26. CSI-TOF mass spectrum of sphere 2c (BF4– salt).

S25


Observed ion


Theoretical mass


Error (ppm)

1221.7923 55675 40461 0.0302 1221.8001 –0.0078 –6.4

1221.8543 58567 39486 0.0309 1221.8626 –0.0083 –6.8

1221.9171 60806 38068 0.0321 1221.9251 –0.0080 –6.5

1221.9803 63946 39704 0.0308 1221.9876 –0.0073 –6.0

1222.0421 66112 39276 0.0311 1222.0501 –0.0080 –6.5

1222.1038 67574 39811 0.0307 1222.1126 –0.0088 –7.2

1222.1670 68875 38897 0.0314 1222.1751 –0.0081 –6.6

1222.2298 68792 38647 0.0316 1222.2376 –0.0078 –6.4

1222.2913 70032 40162 0.0304 1222.3001 –0.0088 –7.2

1222.3535 69283 39505 0.0309 1222.3626 –0.0091 –7.4

1222.4163 66974 37769 0.0324 1222.4251 –0.0088 –7.2

1222.4792 66386 39586 0.0309 1222.4876 –0.0084 –6.9

1222.5411 64800 40715 0.0300 1222.5501 –0.0090 –7.4

1222.6026 61320 38341 0.0319 1222.6126 –0.0100 –8.2

1222.6659 58735 38875 0.0315 1222.6751 –0.0092 –7.5

1222.7289 55732 39193 0.0312 1222.7376 –0.0087 –7.1


Observed ion


Theoretical mass


Error (ppm)

1144.8040 48721 38630 0.0296 1144.8116 –0.0076 –6.6

1144.8626 51374 39090 0.0293 1144.8705 –0.0079 –6.9

1144.9213 54601 39415 0.0291 1144.9293 –0.0080 –7.0

1144.9801 56727 39349 0.0291 1144.9881 –0.0080 –7.0

1145.0388 58743 39132 0.0293 1145.0469 –0.0081 –7.1

1145.0978 60614 38879 0.0295 1145.1057 –0.0079 –6.9

1145.1564 60804 38097 0.0301 1145.1646 –0.0082 –7.2

1145.2150 61674 39012 0.0294 1145.2234 –0.0084 –7.3

1145.2738 61918 39318 0.0291 1145.2822 –0.0084 –7.3

1145.3323 62006 39300 0.0291 1145.3410 –0.0087 –7.6

1145.3916 61043 39262 0.0292 1145.3998 –0.0082 –7.2

1145.4500 59239 39313 0.0291 1145.4587 –0.0087 –7.6

1145.5087 57135 38893 0.0295 1145.5175 –0.0088 –7.7

1145.5673 55601 38736 0.0296 1145.5763 –0.0090 –7.9

1145.6261 52989 39542 0.0290 1145.6351 –0.0090 –7.9

1145.6848 50381 38988 0.0294 1145.6939 –0.0091 –7.9

Table S3. Selected mass information in 16+ and 17+ peaks of 2c (BF4– salt).

S26


2c (BF4– salt).


2c (BF4– salt).

S27

A B C

D E F

G H I

10 8 6 4 10 8 6 4 10 8 6 4 (ppm)

-9.5

-10.0

-10.5

-11.0

-9.5

-10.0

-10.5

-11.0

-9.5

-10.0

-10.5

-11.0

D value

(log D)

Fig. S29. 1H DOSY NMR spectra of mixed-ligand spheres at 1c:3 = (A) 1:9, (B) 2:8, (C) 3:7, (D) 4:6, (E) 5:5, (F) 6:4, (G) 7:3, (H) 8:2, and (I) 9:1 mixing ratio (500 MHz, DMSO-d6, 300 K).

S28

Fig. S30. CSI-TOF mass spectra of mixed-ligand spheres at 1c:3 = (A) 1:9, (B) 2:8, (C) 3:7, (D) 4:6, (E) 5:5, (F) 6:4, (G) 7:3, (H) 8:2, and (I) 9:1 mixing ratio (DMSO/CH3CN = 1:9, OTf– salt). (left) The spectra of M12L24 region and (right) the spectra of M24L48 region.

S29

Empirical Formula C768 H576 F288 N96 O100 P48 Pd24 S48

Formula Weight 23800.29

Temperature 293(2) K

Wavelength 0.70000 Å

Crystal System Tetragonal

Space group I4 (No. 82)

Unit cell dimensions a = 47.527(1) Å, = 90 °

b = 47.527(1) Å, = 90 °

c = 68.663(1) Å, = 90 °

Volume (V) 155097(5) Å3

Z 2

Density (calculated) 0.510 g•cm–3

Absorption Coefficient 0.219 mm 1

F(000) 23680

Crystal Size 0.15 0.15 0.15 mm3

Theta range for data collection 0.51–16.26

Index ranges -36 h 37, 38 k 38, -52 l 54

Reflections collected 95657

Independent reflections 39679 [R(int) = 0.0804]

Completeness to theta = 16.26° 97.8%

Absorption correction None

Max. And min. transmission 0.9680 and 0.9680

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 39679 / 28577 / 1464

Goodness-of-fit on F2 1.701

Final R indices [I>2sigma(I)] R1 = 0.2222, wR2 = 0.4798

R indices (all data) R1 = 0.3199, wR2 = 0.5427

Absolute structure parameter 0.30(7)

Largest diff. peak and hole 1.305 and –0.713 e.Å 3

Table S4. Crystal data and refinement of sphere 2c (PF6– salt).

S30

Fig. S31. Ortep drawing of the asymmetric unit in the crystal structure of 2c (PF6– salt) at

30% probability level.

References for Supporting Materials:

(S1) N. Tanifuji, K. Matsuda, M. Irie, Synthesis of a new diarylethene diradical which has

extended -conjugated chains from the 2,5-position of thiophene ring. Polyhedron,

24, 2484-2490 (2005).

(S2) J. Hou, et al., Bandgap and molecular energy level control of conjugated polymer

photovoltaic materials based on benzo[1,2-b:4,5-b’] dithiophene. Macromolecules,

41, 6012-6018 (2008).

(S3) P. Price, Standard definitions of terms relating to mass spectrometry: a report from the

committee on measurements and standards of the American Society for Mass

Spectrometry. J. Am. Soc. Mass Spectrom. 2, 336-348 (1991).

supporting online material for...2010/04/26 · spectra were measured on a bruker maxis®. the data...

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