本篇研究成功地合成出了四個以 benzophenone 為主架構，並於羰基鄰位接上兩個相同 的推電子基團，造成有立體排開的結構進而降低了其共軛性。四個化合物的熱穩定性於 Tg
上也都表現優良，最高為 LHH1 達 136 ℃，從結晶態溫度也能預期在製成元件時將不會 有產生結晶態，進而降低壽命與效率的衰退。
而四個化合物的放光光色只有 LHH2 在綠光的波段，其餘三個化合物皆是在藍光的波 段。在發光效率上，雖然只有 LHH4 在溶液中的量子產率達 19%，其餘的放光微弱不足 以擔任發光材料，但其卻擁有不小的HOMO 與 LUMO 能階差，這表示其擁有夠小的單重 激發態與三重激發態的能階差；其推電子基團也都有芳香胺類的存在，這使其有較高的 HOMO 能階，加上其 HOMO 與 LUMO 電荷分離的程度相當大，可預期有良好的載子傳遞 能力。
綜合本篇實驗結果，LHH4 在四個化合物中表現最為優良，雖其發光強度不足以擔任 單層的發光材料，但其藍光放光、穩定的熱性質、良好的載子傳遞能力和夠高的HOMO 能階，使其有相當的潛力擔任主體材料。
參考文獻 Scientific, London, 1991.
5. a) VanSlyke, S. A.; Chen, C. H.; Tang, C. W. Appl. Phys. Lett. 1996, 69, 2160. b) Shirota, Y.; Kuwabara, Y.; Inada, H. Appl. Phys. Lett. 1994, 65, 807.
6. a) Wakimoto, T.; Fukada, Y.; Nagayama, Y.; Yokoi, A.; Nakada, H.; Tsuchida, M.
IEEE Trans. Electron. Devices 1997, 44, 1245. b) Stoβel, M.; Staudigel, J.; Steuber.
F.; Blassing, J.; Simmerer, J.; Winnacker, A. Appl. Phys. Lett. 2000, 76, 115. c) Brown, T. M.; Friend, R. H.; Millard, I. S.; Lacey, D. J.; Butler, T.; Burroughes, J.
H.; Cacialli, F. J. Appl. Phys. 2003, 93, 6159.
7. a) Brown, T. M.; Kim, J. S.; Friend, R. H.; Cacialli, F.; Daik, R.; Feast, W. J. Appl.
Phys. Lett. 1999, 75, 1697. b) Salbeck, J.; Yu, N.; Bauer,; WeissGrtel, F.; Bestgen, H. Synth. Met. 1997, 91, 209. c) Shirota, Y.; Okumoto, K.; Inada, H. Synth. Met.
2000, 111, 387. d) Thomas, K. R. J.; Lin, J. T.; Tao, Y. T.; Ko, C. W. J. Am. Chem.
Soc. 2001, 123, 9404.
8. a) Adachi, C.; Tsutsui, T.; Saito, S. Appl. Phys. Lett. 1989, 55, 1498. b) Kido, J.;
Ohtaki, C.; Okuyama, K.; Nagai, K. Jpn. J. Appl. Phys. 1993, 32, L917. c) Agrawal, A. K.; Jenekhe, S. A. Chem. Mater. 1996, 8, 579. d) Wang, C.; Jung, G. Y.;
Batsanov, A. S.; Bryce, M. R.; Petty, M. C. J. Mater.Chem. 2002, 12, 173. e) Aragay, G.; Frontera, A.; Lloveras, V.; Gancedo, J. V.; Ballester, P. J. Am. Chem.
Soc. 2013, 135, 2620. f) Kang, J. W.; Lee, D. S.; Park, H. D.; Park, Y. S.; Kim, J.
W.; Jeong, W. I.; Yoo, K. M.; Go, K.; Kim, S. H.; Kim, J. J. J. Mater. Chem. 2007,
17, 3714.
602. b) Ye, J.; Chen, Z.; Wang, K.; An, F.; Yuan, Y.; Chen, W.; Yang, Q.; Zhang,
ACS Appl. Mater. Interfaces. 2016, 8, 27026.
16. Lee, J.; Yasuda, T. Bull. Chem. Soc. Jpn. 2017, 90, 231.
17. Bredas, J. L.; Silbey, R.; Boudreaux, D. S.; Chance, R. R.; J. Am. Chem. Soc. 1983, 105, 6555.
18. Asokan, T.; Sudarshan, T. J. Appl. Phys. 1994, 75, 3715.
19. Adachi, C. 15
thInternational Symposium on Novel Aromatic Compounds, Taipei, Taiwan, July 28-August 2 (2013).
20. a) Paul, F.; Patt, J.; Hartwig, J. J. Am. Chem. Soc. 1994, 116, 5969. b) Guram, A.;
Buchwald, S. J. Am. Chem. Soc. 1994, 116, 7901. c) Guram, A.; Rennels, R.;
Buchwald, S. Angew. Chem., Int. Ed., 1995, 34, 1348. d) Louie, J.; Hartwig, J.
Ttrahedron. Lett. 1995, 3609. e) Paul, F.; Baranano, D.; Richards, S. f) Hartwig, J. J.
Am. Chem. Soc. 1996, 118, 3626.
21. Dauben, H. J.; McCoy, L. L. J. Am. Chem. Soc. 1959, 81, 4863. Russell, G. A.;
Desmond, K. M. J. Am. Chem. Soc. 1963, 85, 3139.
22. a) Ishiyama, T.; Matsuda, N.; Miyaura, N.; Suzuki, A. J. Am. Chem. Soc. 1993, 115,
11018.; b) Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60, 7508.; c)
Miyaura, N.; Suzuki, A. J. Chem. Soc., Chem. Commun. 1979, 866. d) Miyaura, N.;
Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 3437.
23. Dixon, J. M.; Taniguchi, M.; Lindsey J. S. Photochem. Photobiol. 2005, 81, 212.
24. Jones II, G.; Jackson, W. R.; Choi, C.; Bergmark, W. R. J. Phys. Chem. 1985, 89, 294.
25. Hong, Y.; Lam, J. W. Y.; Tang, B. Z.; Chem. Soc. Rev. 2011, 40, 5361.
26. a) Data, P.; Pander P.; Okazaki, M.; Takeda, Y.; Minakata, S.; Monkman, A. P.
Angew. Chem., Int. Ed. 2016, 55, 5739. b) Furue, R.; Nishimoto, T.; Park, I. S.;
Lee, J.; Yasuda, T. Angew. Chem., Int. Ed. 2016, 55, 7171.
附錄
附圖一、MH 1H NMR (上)、13C NMR (下)
OH
Br Br
附圖二、MK 1H NMR (上)、13C NMR (下)
O
Br Br
附圖三、TTcbz 1H NMR (上)、1H NMR(下)
附圖四、
1H NMR (上)、acridine 1H NMR(下)
附圖五、TPAbr 1H NMR (上)、TPAbpin 1H NMR(下)
N
Br
附圖六、LHH1 1H NMR(上)、13C NMR(下)
O N
N
O N
N
附圖八、LHH3 1H NMR(上)、13C NMR(下)
N N
O
N N
O
附表一、LHH2之晶體結構數據 (一)
Crystal data and structure refinement for
LHH2
.Identification code i16753
Empirical formula C37H28N2O
Formula weight 516.61
Temperature 100.0(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P 21
Unit cell dimensions a = 10.7347(8) Å α= 90°.
b = 7.8760(5) Å β= 106.250(5)°.
c = 16.4807(11) Å γ = 90°.
Volume 1337.72(16) Å3
Z 2
Density (calculated) 1.283 Mg/m3
Absorption coefficient 0.077 mm-1
F(000) 544
Crystal size 0.440 x 0.420 x 0.280 mm3
Theta range for data collection 1.976 to 27.100°.
Index ranges -13<=h<=13, -10<=k<=10, -21<=l<=21
Reflections collected 32352
Independent reflections 5876 [R(int) = 0.0629]
Completeness to theta = 25.000° 100.0 %
Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9705 and 0.8154
Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5876 / 1 / 362
Goodness-of-fit on F2 1.027
Final R indices [I>2sigma(I)] R1 = 0.0388, wR2 = 0.0830
R indices (all data) R1 = 0.0478, wR2 = 0.0888
Absolute structure parameter 0.4(18)
Extinction coefficient n/a
Largest diff. peak and hole 0.172 and -0.187 e.Å-3
O N
N
附表二、LHH2之晶體結構數據 (二)
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for i16753. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________________________
C(28) 6325(3) 5576(3) 4513(2) 25(1)
Bond lengths [Å] and angles [°] for i16753.
_____________________________________________________
C(30)-C(31) 1.388(3)
C(32)-N(1)-C(21) 119.49(19) C(32)-N(1)-C(26) 118.94(19) C(21)-N(1)-C(26) 120.35(18) C(14)-N(2)-C(8) 121.91(19) C(14)-N(2)-C(3) 119.53(19)
C(8)-N(2)-C(3) 118.00(19)
O(1)-C(1)-C(2) 122.4(2)
O(1)-C(1)-C(20) 120.4(2) C(2)-C(1)-C(20) 117.16(19)
C(7)-C(2)-C(3) 118.0(2)
C(13)-C(8)-C(9) 119.7(2) C(13)-C(8)-N(2) 119.7(2)
C(9)-C(8)-N(2) 120.6(2)
C(10)-C(9)-C(8) 120.4(2) C(11)-C(10)-C(9) 120.0(2) C(10)-C(11)-C(12) 119.5(3) C(11)-C(12)-C(13) 121.0(3) C(8)-C(13)-C(12) 119.5(3)
C(19)-C(14)-C(15) 118.7(2) C(19)-C(14)-N(2) 121.6(2) C(15)-C(14)-N(2) 119.6(2) C(16)-C(15)-C(14) 120.3(2) C(15)-C(16)-C(17) 121.1(2) C(16)-C(17)-C(18) 118.9(2) C(19)-C(18)-C(17) 120.6(2) C(18)-C(19)-C(14) 120.3(2) C(25)-C(20)-C(21) 119.1(2) C(25)-C(20)-C(1) 117.8(2) C(21)-C(20)-C(1) 123.1(2) C(22)-C(21)-C(20) 118.6(2) C(22)-C(21)-N(1) 119.3(2) C(20)-C(21)-N(1) 122.1(2) C(23)-C(22)-C(21) 121.4(2) C(22)-C(23)-C(24) 120.4(2) C(25)-C(24)-C(23) 119.0(2) C(24)-C(25)-C(20) 121.5(2) C(31)-C(26)-C(27) 119.5(2) C(31)-C(26)-N(1) 120.4(2) C(27)-C(26)-N(1) 120.1(2) C(28)-C(27)-C(26) 120.0(2) C(27)-C(28)-C(29) 120.6(2) C(30)-C(29)-C(28) 119.4(2) C(29)-C(30)-C(31) 120.3(2) C(26)-C(31)-C(30) 120.3(2) C(37)-C(32)-C(33) 118.6(2) C(37)-C(32)-N(1) 120.9(2) C(33)-C(32)-N(1) 120.5(2) C(34)-C(33)-C(32) 120.2(2) C(35)-C(34)-C(33) 121.1(2) C(34)-C(35)-C(36) 118.9(2) C(35)-C(36)-C(37) 120.6(2) C(36)-C(37)-C(32) 120.4(2)
附表四、LHH2之晶體結構數據 (四)
Anisotropic displacement parameters (Å2x 103)for i16753. The anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ]
C(28) 25(1) 28(1) 18(1) -2(1) 1(1) 2(1)
Crystal data and structure refinement for i16570.
Identification code i16570
Empirical formula C43H36N2O
Formula weight 681.66
Temperature 100.0(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P 21/c
Density (calculated) 1.320 Mg/m3
Absorption coefficient 0.228 mm-1
F(000) 1432
Crystal size 0.318 x 0.272 x 0.224 mm3
Theta range for data collection 2.024 to 27.183°.
Index ranges -28<=h<=28, -10<=k<=10, -26<=l<=26
Reflections collected 115297
Independent reflections 7591 [R(int) = 0.0631]
Completeness to theta = 25.000° 99.9 %
Max. and min. transmission 0.9705 and 0.9008
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 7591 / 0 / 446
Goodness-of-fit on F2 1.044
Final R indices [I>2sigma(I)] R1 = 0.0409, wR2 = 0.0845
R indices (all data) R1 = 0.0593, wR2 = 0.0943
Extinction coefficient n/a
Largest diff. peak and hole 0.260 and -0.432 e.Å-3
附表六、LHH3之晶體結構數據 (二)
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for i16570. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________________________
C(18) 7117(1) -1254(2) 3033(1) 21(1)
Bond lengths [Å] and angles [°] for i16570.
_____________________________________________________
O(1)-C(44) 1.2118(19) N(1)-C(13) 1.409(2)
N(2)-C(22) 1.406(2) C(1)-N(1)-C(16) 118.78(13) C(13)-N(1)-C(16) 117.76(12) C(22)-N(2)-C(34) 120.07(13) C(22)-N(2)-C(38) 117.87(13) C(34)-N(2)-C(38) 119.09(13)
C(2)-C(1)-C(6) 120.31(14)
C(2)-C(1)-N(1) 120.04(14)
C(6)-C(1)-N(1) 119.63(14)
C(3)-C(2)-C(1) 120.35(16)
C(4)-C(3)-C(2) 120.10(16)
C(3)-C(4)-C(5) 119.27(15)
C(4)-C(5)-C(6) 122.32(16)
C(5)-C(6)-C(1) 117.61(15)
C(5)-C(6)-C(7) 122.28(15)
C(1)-C(6)-C(7) 119.72(14)
C(6)-C(7)-C(8) 109.58(13)
C(6)-C(7)-C(15) 112.06(14) C(8)-C(7)-C(15) 111.35(14) C(6)-C(7)-C(14) 107.16(13) C(8)-C(7)-C(14) 107.26(14)
C(15)-C(7)-C(14) 109.22(15) C(9)-C(8)-C(13) 117.78(15)
C(9)-C(8)-C(7) 122.27(15)
C(13)-C(8)-C(7) 119.68(14) C(10)-C(9)-C(8) 121.97(16) C(11)-C(10)-C(9) 119.38(16) C(10)-C(11)-C(12) 120.24(16) C(11)-C(12)-C(13) 120.21(16) C(12)-C(13)-C(8) 120.37(14) C(12)-C(13)-N(1) 120.28(14) C(8)-C(13)-N(1) 119.35(14) C(17)-C(16)-C(21) 120.18(15) C(17)-C(16)-N(1) 119.59(14) C(21)-C(16)-N(1) 120.17(14) C(18)-C(17)-C(16) 120.62(15) C(19)-C(18)-C(17) 119.44(15) C(18)-C(19)-C(20) 120.48(15) C(19)-C(20)-C(21) 120.58(15) C(20)-C(21)-C(16) 118.65(15) C(20)-C(21)-C(44) 120.34(14) C(16)-C(21)-C(44) 120.89(14) C(23)-C(22)-C(27) 119.67(15) C(23)-C(22)-N(2) 120.95(14) C(27)-C(22)-N(2) 119.37(14) C(24)-C(23)-C(22) 120.81(16) C(25)-C(24)-C(23) 119.86(16) C(24)-C(25)-C(26) 119.22(16) C(25)-C(26)-C(27) 122.27(16) C(26)-C(27)-C(22) 117.88(15) C(26)-C(27)-C(35) 122.64(14) C(22)-C(27)-C(35) 119.08(14) C(30)-C(29)-C(34) 117.75(15) C(30)-C(29)-C(35) 122.59(14) C(34)-C(29)-C(35) 119.42(14) C(31)-C(30)-C(29) 122.10(15)
C(33)-C(32)-C(31) 120.19(16) C(32)-C(33)-C(34) 120.45(15) C(33)-C(34)-C(29) 120.19(14) C(33)-C(34)-N(2) 120.51(14) C(29)-C(34)-N(2) 119.30(14) C(29)-C(35)-C(27) 109.09(13) C(29)-C(35)-C(37) 112.90(13) C(27)-C(35)-C(37) 112.88(14) C(29)-C(35)-C(36) 107.26(13) C(27)-C(35)-C(36) 107.12(13) C(37)-C(35)-C(36) 107.26(14) C(43)-C(38)-C(39) 120.13(14) C(43)-C(38)-N(2) 117.42(14) C(39)-C(38)-N(2) 122.33(14) C(40)-C(39)-C(38) 118.54(14) C(40)-C(39)-C(44) 119.05(14) C(38)-C(39)-C(44) 122.38(14) C(41)-C(40)-C(39) 120.94(15) C(42)-C(41)-C(40) 119.92(15) C(41)-C(42)-C(43) 119.65(15) C(38)-C(43)-C(42) 120.79(15) O(1)-C(44)-C(21) 120.48(15) O(1)-C(44)-C(39) 121.04(15) C(21)-C(44)-C(39) 118.48(13) Cl(1)-C(45)-Cl(2) 111.96(9)
附表八、LHH3之晶體結構數據 (四)
Anisotropic displacement parameters (Å2x 103)for i16570. The anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ]
C(29) 15(1) 17(1) 16(1) 0(1) 4(1) -2(1)
Crystal data and structure refinement for i16823.
Identification code i16823
Empirical formula C49H36N2O
Formula weight 668.80
Temperature 100.0(2) K
Wavelength 0.71073 Å
Crystal system Orthorhombic
Space group P 21 21 2
Absorption coefficient 0.074 mm-1
F(000) 704
Crystal size 0.380 x 0.360 x 0.280 mm3
Theta range for data collection 1.764 to 27.086°.
Index ranges -12<=h<=12, -20<=k<=29, -10<=l<=10
Reflections collected 39919
Independent reflections 3949 [R(int) = 0.0411]
Completeness to theta = 25.000° 100.0 %
Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9705 and 0.9014
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 3949 / 0 / 237
Goodness-of-fit on F2 1.058
Final R indices [I>2sigma(I)] R1 = 0.0299, wR2 = 0.0735
R indices (all data) R1 = 0.0314, wR2 = 0.0749
Absolute structure parameter 0.3(5)
Extinction coefficient 0.0060(15)
Largest diff. peak and hole 0.240 and -0.169 e.Å-3
附表十、LHH4之晶體結構數據 (二)
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for i16823. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________________________
C(9) 1854(2) 4882(1) 5275(2) 15(1)
Bond lengths [Å] and angles [°] for i16823.
_____________________________________________________
C(20)-C(25) 1.391(2)
C(21)-C(22) 1.385(2)
C(22)-C(23) 1.387(2)
C(23)-C(24) 1.385(3)
C(24)-C(25) 1.385(2)
C(14)-N(1)-C(11) 121.20(13) C(14)-N(1)-C(20) 119.84(13) C(11)-N(1)-C(20) 118.01(13) O(1)-C(1)-C(2)#1 119.76(9)
O(1)-C(1)-C(2) 119.76(9)
C(2)#1-C(1)-C(2) 120.49(19)
C(7)-C(2)-C(3) 119.68(14)
C(7)-C(2)-C(1) 116.20(14)
C(3)-C(2)-C(1) 124.11(14)
C(2)-C(3)-C(4) 118.54(14)
C(2)-C(3)-C(8) 122.63(14)
C(4)-C(3)-C(8) 118.66(14)
C(5)-C(4)-C(3) 121.18(15)
C(6)-C(5)-C(4) 119.98(15)
C(7)-C(6)-C(5) 119.51(14)
C(6)-C(7)-C(2) 121.04(15)
C(9)-C(8)-C(13) 118.49(14)
C(9)-C(8)-C(3) 121.26(14)
C(13)-C(8)-C(3) 120.20(14)
C(10)-C(9)-C(8) 120.64(15) C(9)-C(10)-C(11) 120.59(15) C(10)-C(11)-C(12) 119.27(14) C(10)-C(11)-N(1) 119.85(14) C(12)-C(11)-N(1) 120.86(15) C(13)-C(12)-C(11) 119.57(15) C(12)-C(13)-C(8) 121.41(15) C(19)-C(14)-C(15) 118.94(14) C(19)-C(14)-N(1) 120.88(14) C(15)-C(14)-N(1) 120.15(14) C(16)-C(15)-C(14) 120.26(15) C(15)-C(16)-C(17) 120.65(16) C(18)-C(17)-C(16) 119.49(15) C(17)-C(18)-C(19) 120.53(16) C(18)-C(19)-C(14) 120.08(15) C(21)-C(20)-C(25) 119.87(15) C(21)-C(20)-N(1) 120.30(14) C(25)-C(20)-N(1) 119.83(14) C(22)-C(21)-C(20) 119.90(15) C(21)-C(22)-C(23) 120.27(15) C(24)-C(23)-C(22) 119.75(16) C(25)-C(24)-C(23) 120.34(15) C(24)-C(25)-C(20) 119.86(15)
附表十二、LHH4之晶體結構數據 (四)
Anisotropic displacement parameters (Å2x 103)for i16823. The anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ]
C(2) 16(1) 13(1) 14(1) 2(1) 3(1) -2(1)