Organic Glass-Forming Materials: 1,3,5-Tris(naphthyl)benzene Derivatives

Supporting Information Organic Glass-Forming Materials: 1,3,5-Tris(naphthyl)benzene Derivatives Paul A. Bonvallet, Caroline J. Breitkreuz, Yong Seol Kim, Eric M. Todd, Katherine Traynor, Charles G. Fry, M. D. Ediger, and Robert J. McMahon* Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706 mcmahon@chem.wisc.edu General Experimental Methods...S2 S3 Synthesis of 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2)...S3 S5 Alternate synthesis of 1,3-bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 )...S6 S8 Notes and References... S9 Table S1. 1 H NMR assignments for compound 2-d 14... S10 Table S2. 13 C NMR assignments for compound 2... S11 Table S3. 13 C NMR assignments for compound 2-d 14... S13 Figure S1. gdq-cosy spectrum (600 MHz) for compound 2... S14 Figure S2. 1 H, 13 C ghsqc spectrum (600 MHz) for compound 2... S15 Figure S3. 1 H, 13 C ghmbc spectrum (600 MHz) for compound 2... S16 Figure S4. gdq-cosy spectrum (600 MHz) for compound 2-d 14... S17 Figure S5. 1 H, 13 C ghsqc spectrum (600 MHz) for compound 2-d 14... S18 Figure S6. 1 H, 13 C ghmbc spectrum (600 MHz) for compound 2-d 14... S19 Figure S7. 2 H spectrum (76.788 MHz) for compound 2-d 14... S20 Figure S8-S16. Scanned NMR spectra...s21-s29 S1

General Experimental Methods. Copper (II) bromide, 2-bromonaphthalene, 1,3,5- tribromobenzene, trimethylborate, 1-naphthylboronic acid, and Pd(PPh 3 ) 4 were purchased from commercial sources and used without further purification. Uncorrected melting points were measured in open capillaries. TLC was carried out using silica gel (60F-254) plates. All glassware was flame-dried and purged with nitrogen prior to use. All reactions were run under a nitrogen atmosphere with stirring, unless otherwise noted. CH 2 Cl 2 was dried over and distilled from CaH 2 immediately prior to use. THF was dried over KOH, predistilled from CaH 2, then distilled from Na/benzophenone immediately prior to use. Hexane and benzene were both distilled immediately prior to use. NMR spectra used to check synthetic reagents and products were acquired at 300 MHz for 1 H or 75 MHz for 13 C{ 1 H}. Higher-field data used for complete NMR assignments were acquired at 500 MHz for 1 H, 125 MHz for 13 C{ 1 H}, 13 C{ 1 H, 2 H}, and 76.8 MHz for 2 H. 1 H 1-D spectra were referenced to internal Me 4 Si at 0.0 ppm. These data were then used to reference the 13 C and 2 H data using the Unified Scale method. 1 For high-field measurements, compound 2 was dissolved to approximately 100 mm in ~600 μl CDCl 3 (with 0.1% v/v Me 4 Si) in a standard 5-mm NMR tube; CHCl 3 was used to dissolve compound 2-d 14. Our INOVA-500 MHz NMR instrument has three full-band rf channels, and the lock channel of the standard, switchable, 2- channel broadband probe was utilized for the 13 C{ 1 H, 2 H} experiments. This same setup was also used for the 13 C{ 2 H} INEPT experiments, acquired in a manner similar to that described by Rinaldi and Baldwin: 2 13 C pw90 = 8.4 μs; 2 H pw90 (on the lock port) = 180 μs, and power level lowered 10 db for 2 H decoupling; J CD = 24.1 Hz, τ = 10.1 ms, Δ = 4.9 ms. 2 H spectra of 2-d 14 were found to not be useful, due to very fast 2 H relaxation (T 1 ~ 21 ms) [Figure S7]. This fast relaxation also prevented the acquisition of 13 C{ 2 H} HETCOR data. An INOVA-600 S2

spectrometer was used to acquire gdq-cosy, HSQC, and HMBC data; relevant parameters are listed in the Figure captions. Mass spectra were recorded on a Micromass AutoSpec mass spectrometer using electron impact. The mass spectra obtained on a MALDI-TOF instrument in reflection mode using anthracene as matrix. Synthesis of 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2). The procedure reported here represents an optimization of that described earlier by Whitaker. 3 1-Bromonaphthalene (6). 4 Naphthalene (5) (1.25 g, 9 mmol) and CuBr 2 adsorbed to alumina (30 g) were added to CCl 4 (88 ml). The solution was stirred for 7 days at 25-29 C, and the reaction progress was followed by 1 H NMR spectroscopy. Upon completion, the reaction mixture was vacuum-filtered, and the filter cake was rinsed with CCl 4 (25 ml). The filtrate was concentrated by rotary evaporation to yield a pale yellow oil, which was subsequently vacuumdistilled. Because residual, sublimed naphthalene was recognized as white crystals in the distillation bridge, the distillation apparatus was changed, and the product 1-bromonaphthalene (6) was collected as a pale yellow oil at 78 C (head temperature, 0.1 mmhg) after a short forerun. 1.28 g (69% yield). 1 H NMR (300 MHz, CDCl 3 ) δ 7.34 (t, 1H), 7.59 (m, 2H), 7.83 (m, 3H), 8.26 (d, 1H). 1-Naphthylboronic acid (9). 3 1-Bromonaphthalene (6) (1.75 ml, 12.6 mmol) was added to THF (18.5 ml), and the solution was cooled to 78 C. n-buli (5.6 ml, 12.6 mmol, 2.24 M in hexane) was added drop-wise to the clear solution, not allowing the temperature to rise above 60 C. After stirring the yellow suspension for 50 min, B(OMe) 3 (2.95 ml, 26 mmol) dissolved in THF (14.5 ml) was added slowly to the reaction mixture, keeping the temperature below 60 C. The solution was allowed to warm up overnight. After cooling the reaction S3

mixture to 5 C, concentrated HCl (5 ml) was added drop-wise to the mixture, keeping the temperature below 7 C. The solution was stirred at room temperature for 1 h, added to water (75 ml), and extracted with ether (3 125 ml). The combined ether extracts were dried over MgSO 4, and the solvent was removed by rotary evaporation. The remaining off-white solids were vacuum-filtered with benzene (4 25 ml) and air-dried for 1.5 h, yielding 1.5 g (69%) of 1-naphthylboronic acid (9) as a white solid (mp 199-200 C). 1 H NMR (300 MHz, Me 2 SO-d 6 ) δ 7.47 (m, 3H), 7.73 (dd, 1H), 7.89 (m, 2H), 8.35 (m, 3H). Because the preparation of 1-naphthylboronic acid (9) is very exothermic, the procedure had to be carried out at low temperature ( 78 C) to avoid overreaction. During the synthesis, a small amount of di-1-naphthylborinic acid was formed, which could be removed by washing the product mixture with benzene. 2-Naphthylboronic acid (11). 3 A solution of 2-bromonaphthalene (3.02 g, 14.6 mmol) in THF (19 ml) was cooled to 78 C. n-buli (2.29 M in hexanes, 6.4 ml, 14.7 mmol) was added slowly, maintaining the temperature below 60 C. After the solution had stirred for 50 min, a separate solution of B(OMe) 3 (3.4 ml, 30.3 mmol) and THF (15 ml) was added slowly. The solution was then allowed to warm to room temperature overnight while stirring. The next day the solution was cooled to 5 C, concentrated HCl (5 ml) was added drop-wise, and the solution was stirred for 1 h. Water (75 ml) was added, and the entire solution was extracted with ether (3 125 ml). The ether extracts were dried with MgSO 4, and the solvent was removed to yield an off-white solid. The solid was isolated via vacuum filtration with benzene (100 ml). After air-drying, 2-naphthylboronic acid (11) was collected as a white solid (1.34 g, 53% yield): 1 H NMR (Me 2 CO-d 6 ) δ 7.50 (m, 2H), 7.90 (m, 4H), 8.45 (s (br), 1H); 13 C NMR (Me 2 CO-d 6 ) δ 126.5, 127.4, 127.41, 128.4, 129.3, 131.3, 133.9, 135.6, 136.0. 5 S4

1,3-Bis(1-naphthyl)-5-(2-naphthyl)benzene (2). 3 A solution of 1,3-dibromo-5-(2- naphthyl)benzene (12) (1.90 g, 5.25 mmol), 1-naphthylboronic acid (9) (2.16 g, 12.6 mmol), 2 M aq. Na 2 CO 3 (11.1 ml, 22.2 mmol), 11 ml EtOH and 60 ml toluene was stirred at RT. After 20 min, Pd(PPh 3 ) 4 (0.459 g, 0.40 mmol, 7.6 mol%) was added and the solution was refluxed for 20 h at 85 C. The orange suspension was allowed to cool to RT. The solution was added to 200 ml water and extracted with CH 2 Cl 2 (2 150 ml, 1 100 ml). The organic layers were combined and dried over MgSO 4, and the solvent was removed (30 C under reduced pressure) to give a light brown solid (4.9 g). This material was purified by flash column chromatography 6,7 (silica, hexane/ch 2 Cl 2, solvent gradient: 49:1 to 9:1, R f = 0.07) and recrystallized from hexane to yield the desired 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2) as a white solid (1.19 g, 50%): mp 194-196 C. 1 H NMR (500 MHz, CDCl 3 ) δ 7.51 (m, 6H), 7.57 (t, J = 7.5 Hz, 2H), 7.62 (dd, J = 7.0 Hz, 1.2 Hz, 2H), 7.69 (t, J = 1.5 Hz, 1H), 7.87 (m, 3H), 7.90 (dt, J = 8.1 Hz, 0.9 Hz, 2H), 7.94 (dd, J = 8.2 Hz, 8.2 Hz, 3H), 7.96 (d, J = 1.5 Hz, 2H), 8.15 (d, J = 8.0 Hz, 2H), 8.18 (d, J = 1.1 Hz, 1H). 13 C NMR (125 MHz, CDCl 3 ) δ 125.4, 125.6, 125.9, 125.99, 126.03, 126.04, 126.2, 126.4, 127.2, 127.6, 127.9, 128.0, 128.2, 128.4, 128.6, 130.7, 131.6, 132.7, 133.7, 133.9, 138.0, 139.9, 141.0, 141.4. Mass spectrum (MALDI-TOF); M + calcd for C 36 H 24 456.2, found 456.4; HRMS cald for C 36 H 24 456.1872, found 456.1877. S5

Alternate Synthetic Pathway for 2-d 14. The Suzuki coupling reactions employed in the synthesis of target compound 2-d 14 may be performed in either order (Scheme S1). The sequence described in the article proceeds via 1,3-dibromo-5-(2-naphthyl)benzene (12) (Scheme S1 top). The alternate pathway, via 1,3-bis(1-naphthyl-d 7 )-5-bromobenzene (14-d 14 ), was also performed (Scheme S1 bottom). In our initial studies, this pathway afforded a lower yield of 2-d 14, so these procedures were not subjected to further optimization. 1,3-Bis(1-naphthyl-d 7 )-5-bromobenzene (14-d 14 ). A solution of 1-naphthylboronic acid-d 7 (9-d 7 ) (2.00 g, 11.2 mmol), 1,3,5-tribromobenzene (10) (1.70 g, 5.6 mmol), 2 M Na 2 CO 3 (12 ml), EtOH (5 ml), and toluene (25 ml) was stirred under N 2 while N 2 was bubbled through S6

the solution with a needle. After 20 min, Pd(PPh 3 ) 4 (477 mg, 0.41 mmol, 7.4 mol%) was added and the solution was refluxed at 85 C for 19 h. The solution was allowed to cool to room temperature and then added to 350 ml of H 2 O. This solution was then extracted with benzene (3 200 ml). The benzene extracts were washed with brine (250 ml), dried with MgSO 4, and solvent was removed to give 3.46 g of a light yellow solid. This material was purified by column chromatography (silica, 8:1 hexane/ch 2 Cl 2, R f = 0.23) to yield the desired product as a white solid (870 mg, 37% yield): mp 124-127 C; 1 H NMR (CDCl 3 ) δ 7.51 (t, J = 2 Hz, 1H), 7.73 (d, J = 2 Hz, 2H); 2 H NMR (38.4 MHz, CH 2 Cl 2 ) δ 7.59 (s (br), 8D) 7.99 (s (br), 6D); 13 C NMR δ 122.2, 125.1, 125.4, 130.5 (s), 131.2, 131.7 (s), 133.6, 138.3, 142.7; mass spectrum m/z (rel intensity) 424 (M +, 5), 422 (M +, 5), 369 (23), 268 (100), 209 (32), 183 (12), 132 (21), 105 (9), 69 (20); HRMS calcd for C 26 H 3 D 81 14 Br 424.1392, found 424.1378. 1-(1-Naphthyl-d 7 )-3,5- dibromobenzene (15-d 7 ) was also isolated from the column (R f = 0.46) as a white solid (580 mg, 28% yield): 1 H NMR (CDCl 3 ) δ 7.62 (d, J = 2 Hz, 2H), 7.78 (t, J = 2 Hz, 1H); 2 H NMR (38.4 MHz, CH 2 Cl 2 ) δ 7.58 (s (br), 4D), 7.95 (s (br), 3D); 13 C NMR δ 122.8, 131.8 (s), 132.8 (s), 144.3; mass spectrum m/z (rel intensity) 371 (M +, 12), 369 (M +, 40), 367 (M +, 12), 314 (42), 235 (14), 209 (54), 136 (100), 107 (40), 68 (36); HRMS calcd for C 16 H 3 D 81 7 Br 2 370.9547, found 370.9512. 1,3-Bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 ). A solution of 1,3-dibromo-5-(2- naphthyl)benzene (14-d 14 ) (2.51 g, 7 mmol), 1-naphthylboronic acid-d 7 (9-d 7 ) (2.51 g, 14 mmol), 2 M Na 2 CO 3 (14 ml), EtOH (15 ml), and toluene (75 ml) was stirred under N 2 while N 2 was bubbled through the solution with a needle. After 20 min, Pd(PPh 3 ) 4 (666 mg, 0.58 mmol, 8.2 mol%) was added and the solution was refluxed at 85 C for 25 h. The solution was allowed to cool to room temperature and added to 200 ml of H 2 O and 200 ml of CH 2 Cl 2. The CH 2 Cl 2 phase was separated and the aqueous phase was extracted with 200 ml of CH 2 Cl 2. The organic S7

extracts were combined, dried with MgSO 4, and solvent was removed to give 4.72 g orange oil. This material was purified by column chromatography (silica, 10:1 hexane/ch 2 Cl 2, R f = 0.12) to yield the desired product as a white solid (1.10 g, 33% yield): mp 192-193 C; 1 H NMR (500 MHz, CDCl 3 ) δ 7.49 (m, 2H), 7.69 (t, J = 1.4 Hz, 1H), 7.87 (m, 3H), 7.94 (d, J = 8.5 Hz, 1H), 7.97 (d, J = 1.7 Hz, 2H), 8.18 (d, J = 1 Hz, 1H). 2 H NMR (76.8 MHz, CHCl 3 ) δ 7.70 (m, 14D); 13 C NMR (125 MHz, CDCl 3 ) δ 125.6, 126.049, 126.051, 126.4, 127.6, 128.0, 128.2, 128.6, 130.7, 131.5, 132.7, 133.69, 133.73, 138.1, 139.8, 141.0, 141.4; mass spectrum m/z (rel intensity) 470 (M +, 51), 446 (8), 393 (21), 322 (77), 238 (57), 236 (56), 210 (24), 208 (25), 157 (66), 129 (100), 128 (75); HRMS calcd for C 36 H 10 D 14 470.2757, found 470.2752. S8

Notes and References (1) Harris, R. K.; Becker, E. D.; Cabral de Menezes, S. M.; Goodfellow, R.; Granger, P., Pure Appl. Chem. 2001, 73, 1795-1818. (2) Rinaldi, P. L.; Baldwin, N. J., J. Am. Chem. Soc. 1983, 105, 7523-7527. (3) Whitaker, C. M.; McMahon, R. J., J. Phys. Chem. 1996, 100, 1081-1090. (4) Kodomari, M.; Satoh, K.; Yoshitomi, S., J. Org. Chem. 1988, 53, 2093-2094. (5) One 13 C NMR resonance is not observed. Presumably, the ipso carbon is not observed due to coupling with 10 B / 11 B. (6) Because of the poor solubility of the sample in the solvent used for column chromatography, an alternate method of loading the sample was used. The sample was dissolved in CH 2 Cl 2 and mixed with a portion of silica gel (1:5 ratio of sample to silica gel). The mixture was evaporated to dryness and loaded atop the chromatography column. (7) Leonard, J.; Lygo, B.; Procter, G., Advanced Practical Organic Chemistry. 2nd ed.; Chapman and Hall: New York, 1995. S9

D D 21 20 19 26 25 D 21 20 19 26 25 D 22 17 18 23 24 D D 22 17 18 23 24 D 9 8 7 12 13 14 D 9 8 7 D 12 13 14 D 10 3 2 11 15 1 16 27 32 31 D 10 3 2 11 15 1 16 27 32 31 4 5 6 28 29 30 36 D 4 5 6 28 D 29 30 36 33 35 34 2 2-d 14 D 33 34 35 Table S1. 1 H NMR assignments for 1,3-bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 ). a Proton δ (ppm) a Intg b Mult J (Hz) COSY c 28 8.177 1.00 d 1.0 32, 31(w) 14, 16 7.965 1.93 d 1.7 12 31 7.935 1.06 d 8.5 32, 28(w) 32 7.875 ~1 dd 8.4, 1.7 28, 31 33, 36 7.868 3.09-1 m 34, 35 12 7.690 0.80 t 1.4 14, 16 34, 35 7.489 2.06 m 33, 36 Chemical shift (δ) from the 1-D spectrum (500 MHz). b Standard integral value. c COSY correlations are given from gdq-cosy spectra; weak crosspeaks are followed by (w). S10

Table S2. 13 C NMR Assignments for 1,3-Bis(1-naphthyl)-5-(2-naphthyl)benzene (2). Carbon δ(ppm) a Int. b hsqc( 1 H δ) J HH (Hz) c hmbc ( 1 H δ) (int) d Proton C-11,C-13 141.41 2.2 7.966 (vw) 7.686 (vw) 14,16 12 7.620 (s) 7.580 (w) 8.179 (m) 28 7.966 (vw) 14,16 7.878 (m) C-15 141.03 1.0 7.938 (vw) 31 7.688 (w) C-1,C-17 139.92 1.9 C-27 138.04 1.0 C-3,C-19 133.87 2.0 C-29 133.68 1.0 C-30 132.73 1.0 8.156 (m) 7.965 (vs) 7.938 (vw) 7.908 (w) 7.965 (vs) 7.938 (s) 8.155 (m) 7.937 (m) 7.906 (m) 8.178 (vw) 7.937 (s) 8.178 (m) 7.936 (w) 8.155 (vw) 7.942 (s) 7.908 (s) 7.687 (vw) 7,23 14,16 10,26 4,20 7.688 (s) 7.620 (w) 7.580 (vs) 6,22 5,21 32 12 12 6,22 5,21 14,16 31 7.876 (w) 32 7,23 7.618 (s) 6,22 10,26 7.579 (vs) 5,21 4,20 7.520 (m) 8,9,24,25 28 31 28 31 7,23 10,26 4,20 12 7.873 (m) 7.490 (m) 7.874 (s) 7.486 (m) 7.618 (s) 7.578 (m) 7.510 (m) 32,33,36 34,35 32,33,36 34,35 6,22 5,21 8,9,24,25 C-2,C-18 131.62 1.7 C-12 130.73 1.7 7.685 s 7.964 (vs) 14,16 7.964 (vs) 14,16 C-31 128.55 2.1 7.933 9.1d 8.178 (vw) 28 7.870 (m) 32?,36,33 C-10,C-26 128.36 3.6 7.937 8.2d 7.907 (s) 4,20 7.503 (s) 8,9,24,25 C-33 128.20 2.1 7.878 7.6d 8.178 (m) 7.870 (w) 28 33,36 7.490 (s) 34,35 C-14,C-16 128.02 3.5 7.964 s 7.966 (vs) 14,16 7.688 (vs) 12 C-4,C-20 127.90 3.7 7.903 8.3d 7.941 (s) 7.619 (m) 10,26 6,22 7.578 (w) 5,21 C-36 127.64 2.0 7.866 7.8d 7.937 (m) 7.880 (w) 31 32 7.490 (m) 34,35 C-6,C-22 127.16 3.8 7.617 7.2d 7.965 (w) 7.908 (s) 16 4,20 7.578 (m) 7.425 (m) 5,21 impurity C-34 [or C-35] 126.37 2.0 7.492 4.6q 7.870 (m) 33,36 7.870 (m) 33,36 C-8,C-24 126.24 3.8 7.497 8.1q 7.941 (s) 7.614 (vw) 10,26 6,22 7.524 (vw) 8,9,24,25 C-28 and C-35 [or C-34] C-7,C-23 126.04 126.03 125.99 3.9 4.0 4.0 8.177 7.484 8.154 5.8q 8.6 7.937 (w) 7.879 (vs) 7.513 (m) 31,10,16 32,33,36 8,9,24,25 C-9,C-25 125.86 3.6 7.519 7.6t 8.156 (m) 7,23 7.492 (vw) 8,9,24,25 C-32 125.56 2.1 7.875 8.8d 8.179 (m) 28 8.179 (m) 28 C-5,C-21 125.43 4.0 7.574 7.7t 7.906 (vw) 7.698 (vw) 4,20 12 7.618 (vw) 7.443 (vw) 6,22 a Chemical shift (δ) from the 13 C{ 1 H} 1-D spectrum (125 MHz); values obtained from ghsqc and HMBC spectra are the same within the digital resolution of the measurements. S11

b c d Intensities are listed from the 13 C{ 1 H} spectrum; the heteronuclear NOEs do affect these intensities. Homonuclear proton-proton couplings measured in the F2 dimension of the ghsqc spectrum. ghmbc cross-peak intensities are indicated by: (vs)-very strong, (s)-strong, (m)-medium, (w)-weak, (vw)-very weak; these intensities qualitatively reflect the closeness (best match provides strongest intensity) of the actual n J HC to the jnxh ( = 8 Hz) used in the experiment. S12

Table S3. 13 C NMR Assignments for 1,3-Bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 ). a b c d Carbon δ (ppm) a Int. b hsqc ( 1 H δ) J HH (Hz) c hmbc ( 1 H δ) (int) d Proton C-11,C-13 141.41 2.0 7.968 (w) 14,16 7.693 (w) 12 C-15 141.04 1.0 8.181 (m) 7.968 (vw) 28 14,16 7.878 (m) 7.693 (w) 32 12 C-1,C-17 139.79 1.5 7.968 (vs) 14,16 7.693 (s) 12 C-27 138.05 1.0 7.968 (vs) 7.939 (s) 14,16 31 7.878 (vw) 32 C-3,C-19 133.73 1.5 8.180 (w) 28 7.869 (m) 33,36 C-29 133.69 1.0 7.937 (s) 31 7.490 (m) 34,35 8.180 (m) 28 7.877 (s) 32 C-30 132.74 1.0 7.937 (m) 31 7.490 (m) 34,35 C-2,C-18 131.53 1.5 7.967 (m) 14,16 7.694 (vw) 12 C-12 130.72 2.0 7.694 s 7.967 (vs) 14,16 C-31 128.55 2.3 7.934 8.8 8.180 (vw) 28 7.870 (m) 32,33,36 C-33 128.22 2.4 7.880 7.4 8.180 (m) 7.870 (w) 28 33,36 7.491 (s) 34,35 C-14,C-16 128.00 4.1 7.969 s 7.969 (vs) 14,16 7.693 (s) 12 C-10 e 127.89 HD 1.3 C-36 127.64 2.3 7.868 7.2 7.938 (m) 31 7.491 (s) 34,35 C-4 e 127.41 HD 1.3 C-6 e 126.72 HD 1.3 7.968 (vw) 14,16 C-34 [or C-35] 126.37 1.9 7.493 4.9 7.872 (m) 33,36 7.491 (vw) 34,35 C-28 126.051 2.0 8.180 s 7.967 (w) 7.937 (m) 14,16 31 7.879 (vs) 7.491 (vw) 32,33 34,35 C-35 [or C-34] 126.049 2.0 7.486 5.8 7.872 (w) 33,36 7.491 (vw) 34,35 C-8 e 125.73 HD 1.3 C-32, C-7 e 125.58 3.1 7.878 8.4 8.180 (s) 28 7.967 (vw) 14,16 C-9 e 125.34 HD 1.3 C-5 e 124.92 HD 1.3 Chemical shift (δ) from 13 C{ 1 H, 2 H} 1-D spectrum (125 MHz); values obtained from HSQC and HMBC spectra are the same within the digital resolution of the measurements. Resonances labeled HD are observed only with simultaneous 1 H and 2 H decoupling, or in the 13 C{ 2 H} INEPT spectrum. Intensities are listed from the 13 C{ 1 H, 2 H} spectrum; 1 H- 13 C heteronuclear NOEs do affect these intensities. Homonuclear proton-proton couplings measured in the F2 dimension of the ghsqc spectrum. ghmbc crosspeak intensities are indicated by: (vs)-very strong, (s)-strong, (m)-medium, (w)- weak, (vw)-very weak; these intensities qualitatively reflect the closeness (best match provides strongest intensity) of the actual n J HC to the jnxh (= 8 Hz) used in the experiment. e Assignments are based on assignments of 2, in conjunction with 2 H isotope shifts (Table 4). S13

Figure S1. gdq-cosy spectrum for 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2) acquired at 600 MHz. Major parameters: np=2048, ni=256, nt=8, d1=3.5, sw=sw1=1.7ppm. Data were processed using π/4-shifted sinebell-squared apodizations in F2 and F1, with final data set sizes of fn=2048 and fn1=1024. 28 7 * 10 * 4 * 14 * 31 { { 32,33,36 { 12 6 * 5 * * * 8,9 34,35 { { F2 (ppm) 7.6 7.7 4:6 * * 4:5 * * 33:34/ 35:36 7.8 7.9 28:31 12:14 * 9:10 * * 8.0 8.1 28:32 7:8 * * 8.2 8.2 8.1 8.0 7.9 7.8 F1 (ppm) 7.7 7.6 7.5 S14

Figure S2. 1 H, 13 C ghsqc spectrum of 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2) acquired at 600 MHz. Major parameters: np=2048, ni=512, nt=4, d1=3.5, sw=1.8ppm, sw1=15ppm, j1xh=155. Data were processed using π/2-shifted sinebell-squared apodizations in F2 and F1, matched to 2 linear prediction in F1, giving final dataset sizes of fn=4096 (zero-filling only) and fn1=2048. F1 (ppm) 126 127 128 129 130 8.2 8.1 8.0 7.9 7.8 F2 (ppm) 7.7 7.6 7.5 S15

Figure S3. 1 H, 13 C ghmbc spectrum of 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2) acquired at 600 MHz. Major parameters: np=4096, ni=512, nt=16, d1=4, sw=1.7ppm, sw1=25ppm, j1xh=140, jnxh=8.0. Data were processed using optimized sinebell gaussian apodizations (peak amplitude ~1/2 through fid) in both F2 and F1, matched to 2 linear prediction in F1, giving final dataset sizes of fn=4096 and fn1=2048. F1 (ppm ) 128 130 132 134 136 138 140 8.2 8.1 8.0 7.9 7.8 F2 (ppm) 7.7 7.6 7.5 S16

Figure S4. gdq-cosy spectrum for 1,3-bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 ) acquired at 600 MHz. Major parameters: np=2048, ni=256, nt=8, d1=3.5, sw=sw1=1.7ppm. Data were processed using π/4-shifted sinebell-squared apodizations in F2 and F1, with final data set sizes of fn=2048 and fn1=1024. 28 14 * 31 32,33,36 12 34,35 F2 (ppm) 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.2 8.1 8.0 7.9 7.8 F1 (ppm) 7.7 7.6 7.5 S17

Figure S5. 1 H, 13 C ghsqc spectrum of 1,3-bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 ) acquired at 600 MHz. Major parameters: np=2048, ni=400, nt=4, d1=3.5, sw=1.42ppm, sw1=20ppm, j1xh=155. Data were processed using π/2-shifted sinebell-squared apodizations in F2 and F1, matched to 2 linear prediction in F1, giving final dataset sizes of fn=2048 and fn1=2048. F1 (ppm ) 126 127 128 129 130 8.2 8.1 8.0 7.9 7.8 F2 (ppm) 7.7 7.6 7.5 S18

Figure S6. 1 H, 13 C ghmbc spectrum of 1,3-bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 ) acquired at 600 MHz. Major parameters: np=2048, ni=400, nt=24, d1=3, sw=1.47ppm, sw1=23ppm, j1xh=140, jnxh=8.0. Data were processed using optimized sinebell gaussian apodizations (peak amplitude ~1/2 through fid) in both F2 and F1, matched to 2 linear prediction in F1, giving final dataset sizes of fn=2048 and fn1=2048. F1 (ppm ) 128 130 132 134 136 138 140 142 8.2 8.1 8.0 7.9 7.8 F2 (ppm) 7.7 7.6 7.5 7.4 S19

Figure S7. 2 H 1-D spectrum of 1,3-bis(1-naphthyl-d 7 )-5-(2-naphthyl)benzene (2-d 14 ) acquired at 76.788 MHz. For this spectrum, a broadband probe was tuned to 2 H, providing optimum sensitivity. Major parameters: nt=128, d1=0, pw=13.2μs, at=0.2s, sw=80ppm. 2 H spin-lattice relaxation was measured separately using inversion-recovery techniques, giving T 1 ~ 21 ms, consistent with the observed linewidths. 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 ppm S20

Figure S8. 2 H NMR 1-D spectrum of 1-bromonaphthalene-d 7 (6-d 7 ) in CHCl 3. Br d 7 S21

Figure S9. 1 H NMR 1-D spectrum of 1-naphthylboronic acid-d 7 (9-d 7 ) + water in Me 2 SO-d 6. 1-naphthylboronic acid-d7 B(OH) 2 d 7 10 8 6 4 2 0 PP S22

Figure S10. 2 H NMR 1-D spectrum of 1-naphthylboronic acid-d 7 (9-d 7 ) in Me 2 CO. B(OH) 2 d 7 S23

Figure S11. 1 H NMR 1-D spectrum of 1,3-dibromo-5-(2-naphthyl)benzene (12) in CDCl 3. 1,3-dibromo-5-(2-naphthyl)benzene Br Br 8.1 8.0 7.9 7.8 7.7 7.6 7.5 PPM 10 8 6 4 2 0 PP S24

Figure S12. 13 C NMR 1-D spectrum of 1,3-dibromo-5-(2-naphthyl)benzene (12) in CDCl 3. 1,3-dibromo-5-(2-naphthyl)benzene Br Br 145 140 135 130 125 PPM 150 100 50 PP S25

Figure S13. 1 H NMR 1-D spectrum of 1-bromonaphthalene (6) in CDCl 3. 1-bromonaphthalene Br 10 8 6 4 2 0 PP S26

Figure S14. 1 H NMR 1-D spectrum of 1-naphthylboronic acid (9) + water in Me 2 CO-d 6. B(OH) 2 1-naphthylboronic acid 8.4 8.2 8.0 7.8 7.6 7.4 PPM 10 8 6 4 2 0 PP S27

Figure S15. 1 H NMR 1-D spectrum of 2-naphthylboronic acid (11) + water in Me 2 CO-d 6. 2-naphthylboronic B(OH) acid 2 8.4 8.2 8.0 7.8 7.6 PPM 10 8 6 4 2 0 PP S28

Figure S16. 13 C NMR 1-D spectrum of 2-naphthylboronic acid (11) in Me 2 CO-d 6. 2-naphthylboronic B(OH) acid 2 136 134 132 130 128 126 PPM 200 150 100 50 0 PP S29