稠环芳烃取代三苯胺双核铱铂配合物电致磷光材料及其应用_3

文档序号:9881013阅读:来源:国知局
2,125.15,125.08,125.05,124.95,124.81,124.77,123.79,123.57,123.30,12325, 123.05,122.73,122.53,122.42,122.27,118.42,114.95,114.66,114.51,114.41,114.27, 109.00. 98·18,97.91,98.78,98.64,97.51,97.25,72.65,70.43,69.92,67.95,43.26, 29.61,29.18,29.02,28.83,27.12,26.09,25.81,25.57。
[0093] MALDI-TOF MS(m/z)for Ci49Hii2F8Ir2N8〇9,理论值:2694.768,测得值,2694·820 〇
[0094] 理论值:Ci49Hii2F8Ir2N8〇9:C 66.41,H 4·19,Ν 4.16。测得值:C 66·26,Η 3·98,Ν 4·32%〇
[0095]环金属铂配合物Β的合成
[0096] 合成方法同Α的合成,得橙红色固体45mg,收率25.3%。1!! NMR(400MHz,CDC13, TMS),δ(ρρπ〇: 4 NMR(400MHz,Me0D)S9.12((1, J = 5.4Hz,2H),8.55((1, J = 5.1Hz,2H) ,8.31 (d,J =9.2Hz,2H) ,8.24-8.14(m,8H),8.10-7.98(m,10H),7.89(d,J = 8.1Hz,2H),7.77(t, J = 7.6Hz,2H) ,7.63-7.53(m,12H) ,7.49-7.43(m,2H) ,7.40-7.31(m,10H) ,7.07(t,J = 6.3Hz,2H) ,6.94(d ,J = 8.4Hz,4H) ,6.77(d ,J = 8.9Hz , 2H), 6.54(t ,J = 10.3Hz , 2H) ,4.48 (s,2H),4.30(t ,J = 4.8Hz,2H),4.14(t ,J = 6.3Hz,4H) ,4.00(t ,J = 6.0Hz ,4H) ,3.52(t ,J = 6.4Hz,2H),2.00-1.90(m,6H),l.87-1.78(m,4H),1.64(d,J=6.1Hz,10H),1.49-1.46(m, 4H). 13CMlR(100MHz,CDCl3,TMS),S(ppm):170.15,163.16,163.11,161.08,160.95, 158.82,158.69,158.05,157.88,149.65,147.04,146.92,142.86,142.79,141.84,141.14, 139.96,139.32,137.38,135.39,134.39,133.72,131.94,131.54,131.52,131.02,130.41, 129.09,128.44,128.10,127.97,127.67,127.48,127.41,127.32,126.02,125.39,125.07, 124.98,124.92,124.79,124.65,123.75,123.48,121.86,121.67,121.42,118.33,114.88, 114.80,114.45,114.28,108.92,99.58,99.32,99.06,72.64,70.42,70.01,67.76,43.15, 29·76,29·61,29·14,28·71,27·11,26·07,25·59,25·37。
[0097] MALDI-TOF MS(m/z)for Ci27Hi〇〇F4N6〇9Pt2,Calcd:2318.678,Found,2341.919[M+ Na]+.理论值:CmHi()()F4N6〇9Pt2:C 65.74,H 4.34,N 3.62.测得值:C 65.49,H 4.15,N 3.85%〇
[0098] 实施例2
[0099] 制备化合物C和D:
[0100] 化合物C和化合物D同核双核环金属铱配合物的合成路线如下所示。
[0103] " y j i
" · *·
[0104] 中间体和配体按与实施例1相同的方法制备。
[0105] 化合物1的合成
[0106]合成方法同实施例1中化合物4的合成。得白色固体产品1.92g,收率78.0% NMR(400MHz,CDC13,TMS),S(ppm):8.76(d,J = 8.0Hz,lH),8.08(d,J = 6.4Hz,lH),7.93(d,J = 8.4Hz,lH),7.83(d,J = 8.0Hz,lH),7.53-7.45(m,3H),1.43(s,12H)。
[0107] 化合物2的合成
[0108] 合成方法同实施例1中化合物9的合成.。得白色粉末产品1.64g,收率71.1 % NMR(400MHz,CDC13,TMS),δ(ρρπ〇: 8.04(d,J = 7.9Hz,2H),7.91((1, J = 7.5Hz,2H),7.85(d,J = 8.0Hz,2H),7.55-7.42(m,12H) ,7.34-7.28(m,8H),4.50(s,2H),3.54(t,J = 6.4Hz,2H), 3.41(t,J=6.8Hz,2H),l.90-1.85(m,2H),l.69-1.64(m,2H),l.47-1.44(m,4H)。
[0109] 化合物3的合成
[0110] 合成方法同实施例1中化合物1 〇的合成。得白色固体产品1.65g,收率71.1 %。4 NMR(400MHz,CDC13,TMS),δ(ρρπ〇: 8.04(d,J = 8.0Hz,4H),7.91((1, J = 7.4Hz,4H),7.85(d,J = 8·0Ηζ,4Η),7· 55-7.40(m,30H),7.29-7.24(m,16H),4.42(s,4H),3.40(t,J = 6.5Hz,4H), 1.94-1.90(m,4H),1.47-1.42(m,4H),1.16-1.09(m,8H),0.59(s,4H).MALDI-TOF MS(m/z) for Ci〇3H86Br2N2〇2,Calcd: 1542.504,Found, 1542.858 〇
[0111] 化合物4的合成
[0112] 合成方法同实施例1中化合物11的合成。得白色固体产品0.78g,收率63.9 %。4 NMR(400 MHz,CDC13,TMS),S(ppm):8.03(d,J = 8.0Hz,4H),7.90((1,J = 7.7Hz,4H),7.84((1, J = 8.0Hz,4H),7.68(d,J = 8.2Hz,2H),7.54-7.45(m,24H),7.40(dJ = 8.2Hz,8H),7.27-7.23(m,16H) ,6.85(d,J = 8.2Hz, 4H) ,4.82( s,2H) ,4.38(s,4H), 3.36( t,J = 6.4Hz,4H), 2.03-1.99(m,4H),1.45-1.42(m,4H),1.11-1.08(m,8H),0.71(s,4H).MALDI-TOF MS(m/z) for C115H96N2O4,Calcd: 1568·737,Found,1568·929〇
[0113] 化合物5的合成
[0114] 合成方法同实施例1中化合物12的合成。得白色固体产品0.52g,收率79.8 %。4 NMR(400MHz,CDC13,TMS),S(ppm):8.25(d,J = 3.7Hz,2H),8.04(d,J = 8.0Hz,4H),7.90(d,J = 7.5Hz,4H),7.84(d ,J = 7.9Hz,4H),7.67(d ,J = 8.1Hz,2H),7.58-7.45(m,24H),7.40(d ,J = 8.3Hz,8H),7.35(d,J = 4.3Hz,2H),7.28(t,J = 8.4Hz,12H),7.23(d,J = 2.4Hz,6H) ,6.97 (d ,J = 8.4Hz,4H),4.38(s,2H) ,4.05-3.96(m, 14H), 3.37(t ,J = 6.5Hz ,4H), 2.05-2.01 (m, 4H),1.86-1.82(m,8H),l.57-1.50(m,8H),l.45-1.42(m,4H),l.16-1.10(m,8H),0.73(s, 4H). 13C 匪R(100MHz,CDC13,TMS),δ(ppm):165.30,158.64,155.02,151.46,147.02, 146.97,140.94,139.96,139.64,135.01,134.18,133.98,133.69,131.75,130.96,128.99, 128.35,128.18,127.46,126.93,126.88,126.13,125.99,125.78,125.65,125.47,124.81, 123·62,121·04,119·91,114·90,72·57,70·61,69·05,67·95,52·48,40·56,29·94,29·92, 29 · 67,29 · 25,28 · 94,25 · 87,25 · 81,25 · 69,23 · 88 ·MALDI-TOF MS(m/z )for C141H130N4O10, Calcd:2038·979,Found,2062·260[M+Na] + 〇
[0115] 化合物6的合成
[0116] 合成方法同实施例1中化合物13的合成。得灰白色固体产品0.37g,收率98.7 %,未 做纯化处理和表征,直接用于配合物的合成。
[0117] 化合物7的合成
[0118] 合成方法同实施例1中化合物10的合成。得黄色固体产品0.82g,收率62.6 %。4 匪R(400MHz,CDC13,TMS),δ(ρρπ〇 :8.32(d,J = 9.2Hz,4H),8.23-8.16(m,12H),8.08-7.99 (m,20H) ,7.57(d,J = 8.1Hz,8H),7.47-7.32(m,22H),4.43(s,4H) ,3.40(t,J = 6.3Hz,4H), 1.94-1.90(m,4H),1.54-1.44(m,4H),1.16-1.08(m,8H),0.60(s,4H).MALDI-TOF MS(m/z) for Ci27H94Br2N2〇2,Calcd: 1838.566,Found, 1838.742〇
[0119] 化合物8的合成
[0120] 合成方法同实施例1中化合物11的合成。得黄色固体产品0.52g,收率46.6 %。4 NMR(400MHz,DMS0,TMS),5(ppm):9.50(s,2H),8.29(t,J=7.6Hz,8H),8.24-8.18(m,16H), 8.11-7.98(m,12H),7.71(d,J=7.8Hz,2H),7.57-7.44(m,16H),7.27-7.17(m,16H),6.82 (d,J = 8.3Hz,4H) ,4.25(s,4H) ,3.17(t,J = 5.8Hz,4H) ,1.99(s,4H) ,1.21-1.16(m,4H), 0.93-0.87(m, 4H), 0.53(s ,4H).MALDI-TOF MS(m/z)for C139H104N2O4, Calcd: 1864.800 , Found,1864.841.
[0121] 化合物9的合成
[0122] 合成方法同实施例1中化合物12的合成。得黄色粉末状产品0.41g,收率61.6% ,Η 匪R(400MHz,CDC13,TMS),δ(ρρπ〇 :8.32(d,J = 9.2Hz,4H),8.28-8.13(m,14H),8.09-7.99 (m,20H),7.70(d,J = 8.2Hz,2H) ,7.57-7.49(m,16H),7.37(d,J = 8.3Hz,8H),7.29(d,J = 6.4Hz,10H) ,7.19(d,J = 8.3Hz,2H) ,6.94(d,J = 8.4Hz,4H) ,4.40(s,4H) ,3.93(d,J = 9.5Hz,14H),3.37(t,J = 6.4Hz,4H) ,2.03(d,J = 6.3Hz,4H) ,1.76(s,8H) ,1.47-1.44(m, 12H),1.16-1.10(m,8H),0.74(s,4H).13CMlR(100MHz,CDC13,TMS),S(pp m):165.25, 158.62,155.03,151.47,146.99,140.85,139.63,139.08,137.47,135.40,134.13,133.83, 131.58,131.54,131.08,130.47,129.10,128.52,128.19,127.70,127.49,127.44,127.36, 126.92,126.05,125.66,125.45,125.13,125.10,125.04,124.99,124.82,124.79,123.74, 121·02,120·93,119·95,114·86,72·58,70·60,68·90,67·89,52·53,40·58,30·39,29·93, 29 · 67,29 · 21,28 · 87,25 · 88,25 · 78,25 · 65,23 · 89 · MALDI-TOF MS(m/z)for Ci65Hi38N4〇io, Calcd:2335.041,Found,2335.152[M]+,2358.113[M+Na]+.
[0123] 化合物10的合成
[0124] 合成方法同实施例1中化合物13的合成。得灰白色固体产品0.29g,收率97.8 %,未 做纯化处理和表征,直接用于配合物的合成。
[0125] 化合物C的合成
[0126] 合成方法同实施例1中化合物六的合成。得黄色固体产品8811^,收率48.9%。1!1匪1? (400MHz,CDC1 3,TMS),δ(ppm) :8.80(d,J = 4.9Hz,2H) ,8.27-8· 20(m,4H),8.03(d,J = 7.7Hz,4H),7.91-7.83(m,8H),7.75-7.68(m,6H),7.52-7.39(m,36H),7.30-7.15(m,22H), 6.95(d,J = 6.8Hz,6H),6.47-6.35(m,4H)
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