Nanographenes as Electron-Deficient Cores of Donor

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Entry Catalyst. Fold of aniline[a]. Phosphine ligand ... Sphos[h]. Cs2CO3 trace[g]. 14. Pd2(dba)3. 4. BrettPhos[j]. Cs2CO3. ND. 15. Pd2(dba)3. 4. Pph3. Cs2CO3.

Nanographenes as Electron-Deficient Cores of Donor-Acceptor Systems Yu-Min Liu1‡, Hao Hou1‡, Yan-Zhen Zhou1, Xin-Jing Zhao1, Chun Tang1, Yuan-Zhi Tan1, Klaus Müllen2 1

Collaborative Innovation Center of Chemistry for Energy Materials, State Key

Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 2

Max Planck Institute for Polymer Research, Ackermannweg 10, D-55128 Mainz,

Germany Correspondence to: [email protected]

Y. M. Liu and H. Hou contributed equally to this work.

1

Supplementary Methods The compounds 2, 4 and 6 were characterized by 1H and 13C NMR spectroscopy, gel permeation chromatography (GPC) analysis, mass spectroscopy and single crystal X-ray diffraction (for 2 and 4). The combustion of large multi-chlorinated polycyclic aromatic hydrocarbons is insufficient, which hinders elemental analysis by combustion method for compounds 2, 4 and 6. Mass spectra of 2, 4 and 6 were acquired on a Bruker microflex LRF MALDI-TOF mass spectrometer using tetracyanoquinodimethane (TCNQ) as the matrix in cation mode. As a supplement, we also tried other softer ionization sources for mass spectroscopy to avoid fragmentation and found that electrospray ionization (ESI) worked for compounds 2a-2d and 4a-4c (Supplementary Figures 6 and 7)as carried out on a Bruker Esquire HCT mass spectrometer (Bruker Corporation). Unfortunately, compounds 2e, 6a and 6b cannot be measured by ESI under the same conditions. All NMR spectra were acquired on a Bruker AV 500M Spectrometer or Bruker AV 600M Spectrometer with a ultra-sensitive Cryo-Probe at room temperature in the solvents indicated. Chemical shifts were expressed in ppm units relative to TMS (0.00 ppm, 1H). Ultraviolet-visible (UV-Vis) spectra in solution were recorded using a Shimadzu UV-2550 Spectrometer. Ultraviolet-visible

(UV-Vis)

spectra

in

solid

state

were

measured

in

a

diffuse-reflectance mode on a Cary 5000 spectrometer. The samples for solid state absorption were prepared by mixing and grinding the crystals of NGs and BaSO4 powder. Using BaSO4 powder as the blank, the absorption spectra of the samples were obtained automatically by the spectrometer. 2

Photoluminescence

spectra

of

2

were

measured

on

a

Hitachi

F-7000

Photoluminescence Spectrophotometer in DCM. Crystallographic data: 2a: The single crystals were grown by slowly diffusing n-hexane into a carbon disulfide solution of 2a. Crystal data: monoclinic, space group P21/n (no. 14), a = 15.8146(5) Å, b = 8.1128(3) Å, c = 26.0032(9) Å, β = 93.023(3)°, V = 3331.6(2) Å3, Z = 2, T = 100.00(10) K, μ(CuKα) = 6.184 mm-1, Dcalc = 1.630 g cm-3, 11425 reflections measured (6.702° ≤ 2Θ ≤ 131.81°), 5621 unique (Rint = 0.0571, Rsigma = 0.0679) which were used in all calculations. The final R1 was 0.0552 (I > 2σ(I)) and wR2 was 0.1571 (all data).

2c: The single crystals were grown by slow evaporation of the carbon disulfide solution of 2c. Crystal data: trigonal, space group R-3 (no. 148), a = 20.7857(12) Å, c = 16.9210(15) Å, V = 6331.2(9) Å3, Z = 3, T = 100.00(10) K, μ(CuKα) = 4.034 mm-1, Dcalc = 1.431 g cm-3, 4261 reflections measured (7.17° ≤ 2Θ ≤ 131.298°), 2354 unique (Rint = 0.0432, Rsigma = 0.0394) which were used in all calculations. The final R1 was 0.0607 (I > 2σ(I)) and wR2 was 0.1759 (all data).

2d: The single crystals were grown by slowly diffusing n-hexane into a carbon disulfide solution of 2d. Crystal data: trigonal, space group R-3 (no. 148), a = 22.3435(15) Å, c = 16.1313(14) Å, V = 6974.3(11) Å3, Z = 3, T = 100.01(10) K, μ(MoKα) = 0.684 mm-1, Dcalc = 1.514 g cm-3, 4226 reflections measured (6.576° ≤ 2Θ ≤ 48.898°), 2439 unique (Rint = 0.0479, Rsigma = 0.1039) which were used in all calculations. The final R1 was 0.0947 (I > 2σ(I)) and wR2 was 0.3118 (all data).

2e: The single crystals were grown by slow evaporation of a carbon disulfide solution of 2e. 3

Crystal data: trigonal, space group R-3 (no. 148), a = 31.5274(8) Å, c = 25.7195(5) Å, V = 22139.5(12) Å3, Z = 9, T = 100.01(10) K, μ(CuKα) = 3.459 mm-1, Dcalc = 1.175 g cm-3, 19889 reflections measured (7.332° ≤ 2Θ ≤ 137.986°), 9120 unique (Rint = 0.0657, Rsigma = 0.0757) which were used in all calculations. The final R1 was 0.0750 (I > 2σ(I)) and wR2 was 0.2129 (all data).

2a⊃TTF: The single crystals were grown by slow evaporation of the carbon disulfide solution of a 1:1 mixture of 2a and TTF. Because carbon disulfide molecules co-crystallized within the crystals, the crystals of 2a⊃TTF easily effloresced what made the diffractions of 2a⊃TTF relatively weak at a high angle. Crystal data: monoclinic, space group C2/c (no. 15), a = 31.629(3) Å, b = 28.3174(17) Å, c = 46.071(3) Å, β = 106.734(7)°, V = 39516(5) Å3, Z = 4, T = 100.01(10) K, μ(CuKα) = 5.458 mm-1, Dcalc = 1.383 g cm-3, 53871 reflections measured (7.42° ≤ 2Θ ≤ 112.86°), 25618 unique (Rint = 0.1653, Rsigma = 0.3273) which were used in all calculations. The final R1 was 0.1171 (I > 2σ(I)) and wR2 was 0.3335 (all data).

4a⊃TTF: The single crystals were grown by slowly diffusing n-hexane into the carbon disulfide solution of 4a and TTF. The crystals of 4a⊃TTF contained carbon disulfide molecules, which made the crystals easy to effloresce when picking and mounting crystals during the measurement. As a result, the diffraction at high angle of crystals of 4a⊃TTF disappeared. Crystal data: triclinic, space group P-1 (no. 2), a = 13.9245(6) Å, b = 19.6503(8) Å, c = 32.4365(15) Å, α = 90.901(4)°, β = 90.656(4)°, γ = 103.718(4)°, V = 8620.0(7) Å3, Z = 2, T = 99.9(4) K, μ(CuKα) = 5.728 mm-1,Dcalc = 1.417 g cm-3, 29448 reflections measured (7.042° ≤ 2Θ ≤ 89.798°), 13553 unique (Rint = 0.0663, Rsigma = 0.0941) which were used in all calculations. The final R1 was 0.1262 (I > 2σ(I)) and wR2 was 0.3240 (all data). 4c⊃TTF: The single crystals were grown by slowly diffusing n-hexane into the carbon disulfide solution of 4c and TTF. 4

Crystal data: triclinic, space group P-1 (no. 2), a = 21.5223(6) Å, b = 23.1734(8) Å, c = 26.4204(6) Å, α = 108.025(3)°, β = 98.092(2)°, γ = 115.886(3)°, V = 10671.0(6) Å3, Z = 2, T = 100.01(10) K, μ(CuKα) = 4.953 mm-1, Dcalc = 1.369 g cm-3, 66796 reflections measured (6.938° ≤ 2Θ ≤ 126.108°), 33436 unique (Rint = 0.0810, Rsigma = 0.0816) which were used in all calculations. The final R1 was 0.0968 (I > 2σ(I)) and wR2 was 0.2866 (all data).

5

Sup pplementarry Figure 1 Thin laayer chromatography (TLC) anaalysis of crude prodducts (spot 1), major component c collected ass 2a (spot 2), 2 subsequeent eluent (spot ( 3), iisolatable byproduct b (sspot 4) and the photo of o silica column after separation. The bypproduct (spoot 4) was obtained by addditional ch hromatograp phic separattion.

Sup pplementarry Figure 2 Synthetic sscheme for 6 from 5.

6

Sup pplementarry Figure 3 GPC anallysis of compounds c 2, 4 annd 6. All the chroomatographhs were acqu uired using a JAIGEL--2H column n eluted by C CHCl3 at a flow ratee of 6 ml/m min, monito ored at 330 nm by a UV-Vis U dettector. All tthe compou unds show wed a sharpp chromatog graphic peaak, confirmiing their purrity. The rettention timees of 2a-22e, 4a-4c and a 6a-6b is 14.95, 1 3.80, 13.50 0, 14.00, 13 3.95, 14.555, 13.40, 13 3.90, 13.225 and 13.80 min, respectively.

7

Sup pplementarry Figure 4 Mass speectra of 2 acquired a on n a Bruker microflex LRF MA ALDI-TOF mass specttrometer ussing TCNQ as the maatrix in cattion mode. The experimental annd calculateed spectra w were represeented in red d and blue, rrespectively y.

8

Sup pplementarry Figure 5 Mass speectra of 4 acquired a on n a Bruker microflex LRF MA ALDI-TOF mass specctrometer uusing TCNQ as matrrix in catioon mode. The experimental annd calculateed spectra w were represeented in red d and blue, rrespectively y.

9

Sup pplementarry Figure 6 Mass speectra of 6 acquired a on n a Bruker microflex LRF MA ALDI-TOF mass specctrometer uusing TCNQ as matrrix in catioon mode. The experimental and a calculateed spectra rrepresented in red and blue, respecctively, fit well. w Thee formula of o 6 can bee assigned as C78Cl200(NHC6H4R) R 6 (R= -C4 H9 for 6a and -OC CH3 for 6b)..

10

Sup pplementarry Figure 7 Mass specctra of 2a-2d acquired on a Brukeer Esquire HCT H masss spectrom meter using ESI E in anionn mode. Th he experimental and cal alculated speectra werre representeed in red an nd blue, resppectively.

11

Sup pplementarry Figure 8 Mass specctra of 4a-4 4c acquired on a Brukeer Esquire HCT H masss spectrom meter using ESI E in anionn mode. Th he experimental and cal alculated speectra werre representeed in red an nd blue, resppectively.

12

Sup pplementarry Figure 9 1H NMR sspectrum off 2a in CD2Cl2. The peeak at 1.50 ppm 1 wass assigned too the signall of water, m marked by asterisk. a H NMR (5000 MHz, CD2Cl2)

δ 7.29 (t, J = 7..9 Hz, 12H)), 7.03 (d, J = 7.8 Hz, 12H), 1 6.98 (t, ( J = 7.4 H Hz, 6H), 6.6 61 (s, 6H)) ppm.

13

Sup pplementarry Figure 10 13C NMR R spectrum of 2a in CD DCl3. 13C N NMR (151 MHz, M CDC Cl3) δ 142.51, 135.86 6, 128.75, 1128.19, 124 4.88, 123.01, 120.63, 118.05, 115.65 ppm m.

14

Sup pplementarry Figure 11 1 1H NMR spectrum of 2b in CDC Cl3. The peaaks at 1.52 ppm wass assigned too the signall of water, m marked by asterisk.1H NMR (5000 MHz, CDC Cl3): δ 7.18 (d, J = 7.5 7 Hz, 12H H), 7.00 (d, J = 8.4 Hz, 12H), 6.61 (s 6H), 2.990 (m, 6H), 1.26 (d, J = 6.3 Hz, 36H) ppm.

15

Sup pplementarry Figure 12 13C NMR R spectrum of o 2b in CD DCl3. 13C N NMR (151 MHz, M CDC Cl3) δ 142..28, 141.31, 137.19, 1129.28, 127 7.09, 125.70 0, 124.07, 118.96, 116 6.83, 33.442, 24.15 pppm.

16

Sup pplementarry Figure 13 1 1H NMR R spectrum of 2c in CD DCl3. 1H NM MR (600 MHz, M CDC Cl3) δ 7.13 (d, J = 8.4 Hz, H 12H), 66.98 (d, J = 8.4 8 Hz, 12H H), 6.60 (s, 66H), 2.59 (tt, J = 6.8 Hz, 12H), 1.64 – 1.58 8 (m, 12H), 1.42 – 1.34 4 (m, 12H), 0.94 (t, J = 7.0 Hz, 18H) 1 ppm m.

17

Sup pplementarry Figure 14 13C NMR R spectrum of 2c in CD DCl3. 13C NM NMR (151 MHz, M CDC Cl3) δ 141..26, 137.22 2, 136.35, 1129.25, 129 9.05, 125.66 6, 124.05, 118.93, 116 6.90, 34.997, 33.77, 22.42, 2 14.00 0 ppm.

18

Sup pplementarry Figure 15 5 1H NMR spectrum of 2d in CDC Cl3. The peaaks at 1.47 ppm 1 wass assigned too the signal of water, m marked by asterisk. a H NMR N (500 M MHz, CDC Cl3) δ

7.000 (d, J = 8.99 Hz, 12H), 6.84 (d, J = 8.9 Hz, 12 2H), 6.52 (s,, 6H), 3.78 ((s, 18H) ppm.

19

Sup pplementarry Figure 16 13C NMR R spectrum of o 2d in CD DCl3. 13C N NMR (151 MHz, M CD2Cl2) δ 1555.58, 138.25 5, 137.72, 1129.12, 125 5.85, 124.57 7, 119.23, 119.21, 114 4.80, 55.992 ppm.

20

Sup pplementarry Figure 17 1 1H NMR R spectrum of 2e in CD DCl3. 1H NM MR (600 MHz, M CDC Cl3) δ 7.02 (d, J = 8.8 Hz, H 6H), 6.776 (d, J = 8.9 Hz, 6H), 6.55 (s, 3H H), 2.92 (s, 18H) 1 ppm m.

21

Sup pplementarry Figure 18 13C NMR R spectrum of 2e in CD DCl3. 13C NM NMR (151 MHz, M CDC Cl3) δ 146..80, 138.01, 134.53, 1128.16, 125 5.12, 124.07 7, 119.25, 118.59, 113 3.99, 41.337 ppm.

22

Sup pplementarry Figure 19 1 1H NMR R spectrum of 4a in C2D2Cl4. The he peaks at 1.52 ppm m and 1.23 ppm were assigned too the signaals of waterr and hexannes, marked d by asteerisks. 1H NMR N (500 MHz, M C2D2 Cl4): δ = 7.36 7 (t, J = 7.84 Hz, 8H H), 7.30 (t,, J = 7.888 Hz, 4H), 6.95-7.20 6 (m m, 18H), 6.881 (s, 4H), 6.65 6 (s, 2H)) ppm.

23

Sup pplementarry Figure 20 0 1H-1H CO OSY spectru um of 4a

24

Sup pplementarry Figure 21 13C NMR R spectrum of o 4a in C2D2Cl4. 13C N NMR (151 MHz, M C2D2Cl4) δ 1422.32, 142.23, 136.33, 135.98, 132 2.55, 129.00 0, 128.93, 128.58, 128 8.27, 125.11, 124.833, 124.65, 124.35, 1223.82, 123.19, 123.09, 122.73, 1121.00, 120 0.79, 119.42, 119.29, 118.29, 11 17.29, 116.009, 115.83 ppm. p

25

Sup pplementarry Figure 22 2 1H NMR R spectrum of 4b in C2D2Cl4. Thee peaks at 1.55 ppm m and 1.22 ppm were assigned too the signaals of waterr and hexannes, marked d by asteerisks. 1H NMR N (500 MHz, M C2D2 Cl4) δ 7.17 (d, J = 8.0 0 Hz, 8H), 77.14 – 7.07 7 (m, 12H H), 6.99 (d, J = 8.0 Hzz, 4H), 2.622 – 2.50 (m m, 12H), 1.39 – 1.31 (m m, 13H), 0.93 – 0.877 (m, 18H). ppm.

26

Sup pplementarry Figure 23 3 1H-1H CO OSY spectru um of 4b in C2D2Cl4

27

Sup pplementarry Figure 24 2 13C NMR R spectrum of 4b in C2D2Cl4. Thee peaks at 29.54 2 ppm m was assiggned to the signal of hhexane, marrked by asteerisk.13C NM MR (151 MHz, M C2D2Cl4) δ 1400.51, 140.43, 137.25, 136.85, 136 6.19, 135.92 2, 132.79, 128.89, 128 8.67, 128.55, 125.277, 125.08, 124.96, 1224.39, 123.75, 123.57, 123.17, 1119.84, 119 9.77, 119.74, 118.655, 117.60, 116.89, 1166.58, 34.50 0, 34.43, 33 3.26, 33.233, 22.04, 21 1.99, 13.666, 13.62 pppm.

28

Sup pplementarry Figure 25 5 1H NMR spectrum of 4c in CD2Cl2. 1H NM MR (600 MH Hz, CD2Cl2) δ 7.199 (d, J = 8.8 Hz, 8H), 7..12 (d, J = 8.8 8 Hz, 4H), 6.96 (d, J = 8.8 Hz, 8H H), 6.922 (d, J = 8.99 Hz, 4H), 3.84 (s, 12H H), 3.81 (s, 6H) 6 ppm.

29

Sup pplementarry Figure 26 13C NMR R spectrum of o 4c in CD D2Cl2. 13C N NMR (151 MHz, M CD2Cl2) δ 1555.88, 155.72 2, 138.94, 1138.53, 137 7.72, 137.60 0, 133.66, 1129.59, 129 9.44, 128.65, 126.133, 125.96, 125.83, 1225.47, 124.88, 124.82, 124.46, 1120.88, 120 0.79, 119.82, 119.75, 119.63, 11 19.46, 118.551, 114.87, 55.99, 5 55.96 6 ppm.

30

Sup pplementarry Figure 27 2 1H NMR R spectrum of 6a in C2D2Cl4. Thee peaks at 1.53 ppm m and 1.24 ppm were assigned a to the signalss of water and a hexaness in the solv vent, marrked by asteerisks. 1H NMR N (500 M MHz, C2D2Cl C 4): δ = 7.11-7.27 (m, 220H), 7.04 (d, J = 7.19 Hz, 4H H,), 6.89 (s, 4H), 6.73 ((s, 2H), 2.5 55-2.64 (m, 12H), 0.888-0.95 (m, 18H) 1 ppm m. Based onn the 1H NM MR spectrum m of 6a, tw wo kinds of anilino grouups with a ratio r of 11:2 can be distiguished, d , suggestingg the C2v sym mmetry of 6a. 6

31

Sup pplementarry Figure 28 2 1H-1H C COSY specttrum of 6a in C2D2Cl44. 1H-1H CO OSY specctrum 6a coonfirmed tw wo kinds of aanilino grou ups with a ratio of 1:2 iin 6a.

32

Sup pplementarry Figure 29 2 13C NMR R spectrum of 6a in C2D2Cl4. Thee peaks at 28.87 2 ppm m was assignned to the signal s of heexanes, marked by asteerisk. 13C NM NMR (151 MHz, M C2D2Cl4) δ 1399.88, 139.87, 136.93, 136.92, 136 6.63, 135.74 4, 135.47, 133.04, 132 2.89, 128.39, 128.388, 128.10, 128.07, 1225.16, 124.7 71, 124.44, 124.32, 1123.85, 123 3.53, 123.37, 123.011, 122.87, 119.58, 1119.46, 119.4 41, 118.87, 118.53, 1117.39, 116 6.53, 116.23, 34.15,, 34.08, 32 2.88, 32.844, 21.71, 21.65, 13.24 4, 13.20 pppm. t C2v symm mmetry of 6a a. specctrum of 6aa validated the

33

13

C NMR N

Sup pplementarry Figure 30 3 1H NMR R spectrum of 6b in CD D2Cl2 1H-NM MR (500 MHz, M CD2Cl2): δ = 7.21 (8H, d, J = 9.95 Hzz), 7.10 (d, J = 9.17 Hzz, 4H), 6.95 (d, J = 8.00 0 Hz, 8H)), 6.88 (d, J = 8.19 Hzz, 4H), 6.888(t, J = 7.46 Hz, 6H), 3.80(s, 12H H), 3.76(s, 6H) ppm m. Based onn the 1H NM MR spectrum m of 6b, tw wo kinds of anilino grouups with a ratio r of 11:2 can be distinguished d d, suggestinng the C2v sy ymmetry off 6b.

34

Sup pplementarry Figure 31

The cryystal structu ure of 2c

Sup pplementarry Figure 32 2

The cryystal structu ure of 2d

pplementarry Figure 33 3 Sup

The cryystal structu ure of 2e

35

Sup pplementarry Figure 34 4

The cryystal structu ure of 4c⊃T TTF.

36

2a Absorption (a.u.)

Cyclohexane Toluene DCM CHCl3 THF DMF DMSO

300

400

500

600

700

800

Wavelength (nm) Supplementary Figure 35 UV-Vis spectra of 2a in various solvents with increasing polarity (the concentration of the solution is 5×10-6 mol L-1). The redshift is about 13 nm from the most nonpolar solvent (cyclohexane) to the most polar solvent (DMSO).

2a Absorption (A)

1.0

0.5

0.0 300

400

500

600

700

800

Wavelength (nm) Supplementary Figure 36 UV-Vis spectra of 2a at variable concentrations from 1.1×10-6 mol L-1 to 16.7×10-6 mol L-1 in DCM solution. 37

2b

Absorption (A)

1.0

0.5

0.0 300

400

500

600

700

800

Wavelength (nm) Supplementary Figure 37 UV-Vis spectra of 2b at variable concentrations from 1.1×10-6 mol L-1 to 13.2×10-6 mol L-1 in DCM solution.

2c Absorption (A)

1.0

0.5

0.0 300

400

500

600

700

800

Wavelength (nm) Supplementary Figure 38 UV-Vis spectra of 2c at variable concentrations from 1.0×10-6 mol L-1 to 11.7×10-6 mol L-1 in DCM solution.

38

2d Absorption (A)

1.5

1.0

0.5

0.0 300

400

500

600

700

800

Wavelength (nm)

Supplementary Figure 39 UV-Vis spectra of 2d at variable concentrations from 1.2×10-6 mol L-1 to 14.2×10-6 mol L-1 in DCM solution.

2e Absorption (A)

1.0

0.5

0.0

300

400

500

600

700

800

Wavelength (nm)

Supplementary Figure 40 UV-Vis spectra of 2e at variable concentrations from 0.6×10-6mol L-1 to 7.2×10-6 mol L-1 in DCM solution.

39

Intensity (a.u.)

2a 2b 2c 2d 2e

500

550

600

650

700

Wavelength (nm) Supplementary Figure 41 Photoluminescence spectra of 2a (black), 2b (red), 2c (blue), 2d (olive), and 2e (navy) in DCM (concentration is 2×10-6mol L-1).

40

Sup pplementarry Figure 42 2 Intermoleecular interaactions (reprresented byy dashed cyaan linees) in the cryystal packin ng of 2a (a),, 2c (b), 2d (c) and 2e (d). (

41

Absorption (a.u.)

2a

570

300

400

500

605

600

700

800

Wavelength (nm) Supplementary Figure 43 UV-Vis spectra of 2a in the solid state (red) and in DCM solution (blue, 10-5 mol·L-1).

Absorption (a.u.)

2b

612 578

300

400

500

600

700

800

Wavelength (nm)

Supplementary Figure 44 UV-Vis spectra of 2b in the solid state (red) and in DCM solution (blue, 10-5 mol·L-1).

42

Absorption (a.u.)

2c

571

300

400

500

600

600

700

800

Wavelength (nm) Supplementary Figure 45 UV-Vis spectra of 2c in the solid state (red) and in DCM solution (blue, 10-5 mol·L-1).

Absoprtion (a.u.)

2d

611 580

300

400

500

600

700

800

Wavelength (nm) Supplementary Figure 46 UV-Vis spectra of 2d in the solid state (red) and in DCM solution (blue, 10-5 mol·L-1).

43

Sup pplementarry Figure 47 UV-Vis ab absorption sp pectra of 3 (C60Cl22) inn DCM solu ution (10--5 mol L-1).

5

 mol-1cm-1L)

1.5x10

4a 4b 4c

5

1.0x10

4

5.0x10

0.0 0 300

400

500

600

700

800

Wa avelength h (nm) Sup pplementarry Figure 48 8 UV-Vis abbsorption sp pectra of 4a a (black), 4bb (red) and 4c -5 -1 (bluue) in DCM solution (10 mol L )).

44

5

6a 6b

5

1.0x10

-1

-1

 mol cm L)

1.5x10

4

5.0x10

0.0 300 0

400

500

600 0

700

800

Wavelength (n nm)

Sup pplementarry Figure 49 9 UV-Vis abbsorption sp pectra of 6a a (black) andd 6b (red) in -5 -1 DCM M solution (10 mol L ).

Sup pplementarry Figure 50 0 UV-Vis-N NIR spectra of 4c and 2·4c⊃TTF 2 inn the solid state acquuired in a diffuse-reflecctance modde.

45

Sup pplementarry Figure 51 Numberinng of the carbon atoms of 2a

Sup pplementarry Figure 52 2

Visualiization of frrontier moleecular orbitaals of 2 46

Sup pplementarry Figure 53 The eelectron deensity differences betw tween the first exciitation statee and the grround state of 2 (a, 2a a, b, 2b, c, 2c, 2 d, 2d annd e, 2e). (B Blue and red refer too a decreasee and an incrrease in electron densitty, respectivvely)

47

Sup pplementarry Figure 54 4 Visualizattion of fron ntier molecu ular orbitals of 4

Sup pplementarry Figure 55 The eelectron deensity differences betw tween the first exciitation statee and the gro ound state oof 4 (a, 4a, b, b 4b and c,, 4c). (Blue and red reffer to a deecrease and an increasee in electronn density, reespectively)

48

Supplementary Table 1 Condition screening for the C-N coupling of 1 to aniline Entry

Catalyst

1

Pd2(dba)3

2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3 Pd2(dba)3

Fold of aniline[a] 4 1 1.5 15 30 4 4 4 4 4 4 4 4 4 4 4 4 4

Phosphine ligand

Base

rac-BINAP[b]

Cs2CO3

rac-BINAP rac-BINAP rac-BINAP rac-BINAP rac-BINAP rac-BINAP Dppf[d] Xantphos[e] Bis(diphenylphosphino)methane 1,2-Bis(diphenylphosphino)ethane X-phos[f] Sphos[h] BrettPhos[j] Pph3 (t-Bu)3P Trihexylphosphine IMes•HCl[k]

Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 K2CO3 tBu-OK Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3 Cs2CO3

Yield 31% (50%[c]) 15% 18% 30% 31% ND ND 13% 15% ND ND trace[g] trace[g] ND ND ND ND ND

[a] according to the molar of chlorine at the vertexes of 1 [b] (±)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene; [c] calculated by NMR spectroscopy [d] 1,1'-Ferrocenebis(diphenylphosphine); [e] 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene; [f] 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl; [g] detected by TLC [h] 2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl; [j] 2-(Dicyclohexylphosphino)-3,6-dimethoxy-2'-4'-6'-tri-i-propyl-1,1'-biphenyl; [k] 1,3-Bis(2,4,6-trimethylphenyl)imidazolium chloride;

49

Supplementary Table 2 Absorption and photoluminescence data of 2a-2e

4

-1

Stoke shift

λmax(em)

λmax(abs) (nm)[a]

(nm)

[a,b]

-1

PLQY

(cm )

(%)

[c]

Eg,opt (eV)[d]

-1

[ε(×10 Lmol cm )] 2a

443 (6.3)

558

4652

3.14

2.18

2b

443 (7.3)

558

4652

3.55

2.18

2c

443 (9.0)

561

4748

5.45

2.15

2d

456 (10.6)

575

4539

-

2.10

2e

478 (14.0)

-

-

-

1.84

[a] in DCM. [b] excitation wavelength: 443 nm for 2a; 443 nm for 2b; 443 nm for 2c; 456 nm for 2d. [c] Absolute photoluminescence quantum yield (PLQY) was determined by a calibrated integrating sphere. system. The PLQY of 2d and 2e is too low to be determined. [d] Optical HOMO-LUMO gaps were estimated from the onset of the absorption spectra

Supplementary Table 3 Absorption data of 3, 4a-4c, 5, 6a and 6b λmax(abs) (nm)[a]

Eg,opt (eV)[b]

[ε(×104 cm-1 M-1)] 3 4a 4b 4c 5 6a 6b

446 (7.42) 471 (13.9) 473 (17.6) 479 (14.0) 463 (null) 500 (16.7) 502 (14.0)

2.11 1.98 1.95 1.94 1.93 1.72 1.78

[a] in CH2Cl2 . [b] Optical HOMO-LUMO gaps were estimated from the onset of the absorption spectra.

50

Supplementary Table 4 Comparison of theoretically calculated G and Gopt, exp.. Gopt, exp. GB3LYP GCAM-B3LYP GM062X GHSEH1PBE (eV)

(eV)

(eV)

(eV)

(eV)

2.15

2.73

4.91

4.51

2.33

4b 1.95

2.37

4.43

4.03

1.96

2c

Supplementary Table 5 Comparison of the bond lengths (BL) between experimental data (crystal structure) and theoretically optimized structure of 2a and relative deviations (RD) (See Supplementary Figure 51). C1-C1’

C1-C2

C2-C3

C3-C3’

C3-C4

C4-C5

RD

(Å)

(Å)

(Å)

(Å)

(Å)

(Å)

(%)[a]

Experimental

1.412

1.435

1.420

1.459

1.403

1.402

0

B3LYP

1.415

1.439

1.423

1.471

1.407

1.414

0.44%

CAM-B3LYP

1.406

1.442

1.413

1.470

1.400

1.406

0.44%

M062X

1.409

1.444

1.412

1.469

1.402

1.408

0.43%

HSEH1PBE

1.410

1.434

1.416

1.463

1.404

1.410

0.23%

[a]

RD = Σ[(|BLoptimized – BLexperimental|)/BLexperimental]/n.

51

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