CN110818743B - 一种具有聚集诱导发光性质的环金属铂配合物的制法及应用 - Google Patents
一种具有聚集诱导发光性质的环金属铂配合物的制法及应用 Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
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- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 claims description 4
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
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- 238000012512 characterization method Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 238000010791 quenching Methods 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
一种具有聚集诱导发光性质的环金属铂配合物的制法及应用,其属于光电材料技术领域。本发明以烷基修饰的2‑苯基吡啶为环金属配体,以1,10‑菲啰啉为辅助配体合成了环金属铂配合物,对其光物理性质进行测试。本发明制备的铂配合物具有显著的聚集诱导发光性质,其在光电材料领域有重要应用价值。
Description
技术领域
本发明涉及一种具有聚集诱导发光性质的环金属铂配合物的制法及应用,其属于光电材料技术领域。
背景技术
传统荧光分子通常在稀溶液中具有强烈荧光,在高浓度下荧光会减弱甚至猝灭。2001年,唐本忠等发现一种小分子发光染料在稀溶液中基本没有荧光,而在聚集态时呈现明亮的荧光发射(Chem. Commun., 2001, 18, 1740-1741),他们将这一新的现象称为聚集诱导发光(Aggregation-Induced Emission,简写AIE)。聚集诱导发光现象的发现为解决聚集导致发光猝灭这一重大科学问题提供了一条有效的思路,极大地推动了高效率固态发光材料的应用和发展。迄今,见诸文献的AIE分子大多为纯有机小分子,基于过渡金属配合物的新型聚集诱导磷光发射(Aggregation-Induced Phosphorescent Emission,简写AIPE)的材料尤其是铂配合物的报道相对较少。环金属铂配合物作为一种磷光材料,已广泛应用于OLED (Chem. Rec., 2019, 19, 1693-1709; Adv. Sci., 2019, 6, 1801930; Adv. Optical Mater., 2018, 1800466),光学传感器(Talanta, 2018, 186, 36-43; J. Mater. Chem. C, 2018, 6, 8999-9009),细胞成像(J. Organomet. Chem., 2017, 835,25-30; J. Mater. Chem. C, 2019, 7, 7893-7899)等领域,因此,创制具有优良的聚集诱导发光性质的结构简单、制备简便的环金属铂配合物具有重要的应用价值。
发明内容
本发明的目的是提供一种烷基修饰的环金属铂配合物Pt1和Pt2的制备方法及其聚集诱导发光性质。
本发明采用的技术方案是:一种烷基修饰的环金属铂配合物,由4-甲基苯硼酸或4-乙基苯硼酸与2-溴吡啶合成的CÙN型环金属配体与1,10-菲啰啉共同络合铂金属离子,最后经过置换阴离子制得,其结构如下:
所述烷基修饰的环金属配体与铂配合物的制备方法,具体合成步骤如下:
(1) C^N型环金属配体的合成:在空气中,向反应瓶中依次加入2-溴吡啶(1.0mmol)、芳基硼酸(1.2 equiv.)、碳酸钾(2.0 equiv.)、醋酸钯(1.5% equiv.),然后加入体积比为3:1的乙醇-水混合溶液8 mL,在80 ℃磁力搅拌进行Suzuki交叉偶联反应,由薄层色谱跟踪反应进程,反应完全后,用二氯甲烷萃取三次,合并有机相,减压浓缩,经柱层析分离,制得C^N型环金属配体。
(2) 铂配合物的合成:向反应瓶中加入C^N型环金属配体和1.2当量的K2PtCl4,在分别除氧的体积比为3:1的乙二醇单乙醚/水混合溶液中,N2保护条件下,于105 °C磁力搅拌反应24 h,反应结束后,减压浓缩反应液,得到二氯桥中间产物。将二氯桥中间产物、2.0当量的1,10-菲啰啉加入反应瓶中,以无水乙二醇单乙醚为溶剂,在氮气氛围下,于105 °C加热回流24 h。反应结束后,冷却至室温,再加入20 mL KPF6饱和水溶液,室温搅拌12 h。用20 mL二氯甲烷萃取3次,将收集的有机相减压浓缩得粗产品;以二氯甲烷/甲醇为洗脱剂,经柱层析分离,纯化得到目标产物,产物结构通过1H NMR、13C NMR和质谱鉴定。
上述环金属铂配合物包括下列衍生物:
化合物Pt1:芳基硼酸选自4-甲基苯硼酸;
化合物Pt2:芳基硼酸选自4-乙基苯硼酸。
本发明的有益效果:
1.烷基修饰的环金属铂配合物通过模块化设计,在2-苯基吡啶的苯环的4位引入甲基、乙基,可获得具有优良聚集诱导发光性质的铂配合物。
2.以Suzuki交叉偶联反应合成环金属配体的方法环境友好、简便高效。
附图说明
图1是本发明化合物Pt1溶液中的紫外-可见吸收光谱图(溶剂为乙腈,10-5 mol/L)。
图2是本发明化合物Pt1在不同水含量下的发射光谱图(溶剂为乙腈/水,5 ´ 10-5 mol/L)。
图3是本发明化合物Pt2溶液中的紫外-可见吸收光谱图(溶剂为乙腈,10-5 mol/L).
图4是本发明化合物Pt2在不同水含量下的发射光谱图(溶剂为乙腈/水,5 ´ 10-5 mol/L)。
具体实施方式
实施例1 化合物Pt1的合成
(1) 环金属配体的合成:
向反应瓶中依次加入2-溴吡啶(1.0 mmol)、4-甲基苯硼酸(1.5 mmol)碳酸钾(2.0mmol)、醋酸钯(0.015 mmol),然后加入体积比为3:1的乙醇-水混合溶液8 mL,在80 ℃磁力搅拌进行Suzuki反应,由薄层色谱跟踪反应进程,反应完全后,加入饱和食盐水20 mL,用20mL二氯甲烷萃取3次反应产物,合并有机相,减压浓缩,经柱层析分离,制得C^N型环金属配体,产率85%。结构表征数据如下:1H NMR (400 MHz, CDCl3) δ 8.71 (d, J = 4.7 Hz,1H), 7.92 (d, J = 8.2 Hz, 2H), 7.75 (dd, J = 11.9, 4.9 Hz, 2H), 7.31 (d, J =8.0 Hz, 2H), 7.23 (ddd, J = 6.6, 4.9, 1.8 Hz, 1H), 2.44 (s, 3H).
(2) 铂配合物的合成:
向反应瓶中加入C^N型环金属配体和1.2当量的K2PtCl4,在分别除氧的体积比为3:1的乙二醇单乙醚/水混合溶液中,N2保护条件下于105 °C磁力搅拌,反应24 h,反应结束后,减压浓缩反应液,得到二氯桥中间产物。将二氯桥中间产物、2.0当量的1,10-菲啰啉加入到12 mL无水乙二醇单乙醚中,在氮气氛围下于105 °C加热回流24 h。反应结束后,冷却至室温,再加入20 mL KPF6饱和水溶液,室温搅拌12 h。将反应液用20 mL二氯甲烷萃取3次,减压浓缩得粗产品,以二氯甲烷/甲醇为洗脱剂,经柱层析分离,纯化得到目标产物,产率43%。结构表征数据如下:1H NMR (400 MHz, DMSO-d 6): δ 9.44 (d, J = 4.8 Hz, 1H),9.16 (d, J = 4.1 Hz, 1H), 8.76 (d, J = 4.2 Hz, 2H), 8.55 (d, J = 5.4 Hz, 1H),8.13 (d, J = 2.5 Hz, 2H), 7.99 (d, J = 7.6 Hz, 2H), 7.84 (dd, J = 16.2, 8.0Hz, 2H), 7.49 (d, J = 7.9 Hz, 1H), 7.18 – 6.94 (m, 2H), 6.82 (s, 1H), 6.68(d, J = 7.8 Hz, 1H), 2.25 (s, 3H). 13C NMR (400 MHz, DMSO-d 6): δ 170.03,157.14, 154.54, 154.10, 150.70, 148.74, 146.28, 144.80, 144.28, 144.10,144.03, 137.48, 134.80, 132.90, 132.72, 130.78, 130.15, 128.13, 127.59,123.79, 26.86. HRMS (MALDI-TOF, m/z): 计算值:C24H18F6N3PPt [M - PF6]+ 543.1148;实测值:543.1138。
实施例2 化合物Pt2的合成
(1)环金属配体的合成:
向反应瓶中依次加入2-溴吡啶(1.0 mmol)、4-乙基苯硼酸(1.5 mmol)碳酸钾(2.0mmol)、醋酸钯(0.015 mmol)和体积比为3:1的乙醇/水混合溶液12 mL。在80 °C磁力搅拌进行Suzuki交叉偶联反应,反应进程由薄层色谱跟踪。反应完全后,加入饱和食盐水20 mL,用20 mL二氯甲烷萃取反应产物3次,合并有机相,使用旋转蒸发仪浓缩得到粗产品,以石油醚和乙酸乙酯为洗脱剂,经柱层析分离,得到目标产物,产率90%。结构表征数据如下:1H NMR(400 MHz, CDCl3) δ 8.68 (d, J = 4.9 Hz, 1H), 7.92 (d, J = 8.2 Hz, 2H), 7.72(d, J = 1.5 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 7.21 (ddd, J = 6.7, 4.9, 2.0Hz, 1H), 2.71 (q, J = 7.6 Hz, 2H), 1.28 (t, J = 7.6 Hz, 4H)。
(2) 铂配合物的合成:
向反应瓶中加入C^N型环金属配体和1.2当量的K2PtCl4,在分别除氧的体积比为3:1的乙二醇单乙醚/水混合溶液中,N2保护条件下于105 °C磁力搅拌,反应24 h,反应结束后,减压浓缩反应液,得到二氯桥中间产物。将二氯桥中间产物、2.0当量的1,10-菲啰啉加入到12 mL无水乙二醇单乙醚中,在氮气氛围下于105 °C加热回流24 h。反应结束后,冷却至室温,再加入20 mL KPF6饱和水溶液,室温搅拌12 h。将反应液用20 mL二氯甲烷萃取3次,减压浓缩得粗产品,以二氯甲烷/甲醇为洗脱剂,经柱层析分离,纯化得到目标产物,产率45%。结构表征数据如下:1H NMR (400 MHz, DMSO-d 6): δ 9.15 (d, J = 4.7 Hz, 1H),8.92 (d, J = 4.3 Hz, 1H), 8.70 – 8.39 (m, 2H), 8.27 (d, J = 5.2 Hz, 1H), 7.98(d, J = 5.1 Hz, 2H), 7.86 – 7.73 (m, 1H), 7.68 – 7.55 (m, 2H), 7.18 (d, J =8.0 Hz, 1H), 6.89 – 6.71 (m, 2H), 6.66 – 6.45 (m, 2H), 2.43 (q, J = 7.5 Hz,2H), 1.18 (t, J = 7.6 Hz, 3H). 13C NMR (500 MHz, DMSO-d 6): δ 165.09, 151.95,149.15, 145.74, 145.09, 143.74, 141.75, 139.79, 139.29, 139.04, 131.19,129.76, 127.80, 127.56, 125.87, 125.81, 123.80, 123.40, 122.55, 118.81,28.35, 15.06. HRMS (MALDI-TOF, m/z): 计算值:C25H20F6N3PPt [M - PF6]+ 557.1305;实测值:557.1309。
实施例3 化合物Pt1的光物理性质测试
将化合物Pt1溶于乙腈中配制成浓度为1 × 10-5 mol/L的溶液,测试其紫外-可见吸收光谱(图1)。再将乙腈溶解的样品溶液、乙腈和水按照不同的体积比混合,形成含水量不同的混合溶液(Pt1的浓度为5 × 10-5 mol/L),随后测试其发射光谱(图2)。图2结果表明,在乙腈/水混合溶液中,随着不良溶剂水的含量增加,化合物的发光逐渐增强,至水含量为90%时发射强度达到最大。该结果表明化合物Pt1具有优良的聚集诱导发光性质。
实施例4 化合物Pt2的光物理性质测试
将化合物Pt2溶于乙腈中配制成浓度为1 × 10-5 mol/L的溶液,测试其紫外-可见吸收光谱(图3)。再将乙腈溶解的样品溶液、乙腈和水按照不同的体积比混合,形成含水量不同的混合溶液(Pt2的浓度为5 × 10-5 mol/L),随后测试其发射光谱(图4)。图4结果表明,在乙腈/水混合溶液中,随着不良溶剂水的含量增加,化合物的发光逐渐增强,至水含量为90%时发射强度达到最大。该结果表明化合物Pt2具有优良的聚集诱导发光性质。
Claims (3)
2.根据权利要求1所述的一种具有聚集诱导发光性质的环金属铂配合物的制备方法,其特征在于:所述环金属铂配合物的合成步骤如下:
(1) 环金属配体的合成:以4-甲基苯硼酸或4-乙基苯硼酸与2-溴吡啶为起始剂,碳酸钾为碱,醋酸钯为催化剂,在无外加配体的条件下,于空气中发生Suzuki交叉偶联反应,由薄层色谱跟踪反应进程,反应完全后,经柱层析分离得到环金属配体;
(2) 铂配合物的合成:向反应瓶中加入环金属配体和1.2当量的K2PtCl4,在体积比为3:1的乙二醇单乙醚/水混合溶液中,于氮气中及105℃磁力搅拌反应24 h,反应结束后,减压浓缩反应液,得到二氯桥中间产物;将二氯桥中间产物、2.0当量的1,10-菲啰啉加入反应瓶中,以无水乙二醇单乙醚为溶剂,在氮气氛围下,于105℃加热回流24 h;反应结束后,冷却至室温,再加入20 mL KPF6饱和水溶液,室温搅拌12 h;用20 mL二氯甲烷萃取3次,将收集的有机相减压浓缩得粗产品;以二氯甲烷/甲醇为洗脱剂,经柱层析分离,纯化得到目标产物。
3.根据权利要求1所述的一种具有聚集诱导发光性质的环金属铂配合物非疾病诊断和治疗目的的应用,其特征在于:所述环金属铂配合物应用于化学传感、光电领域、生物荧光探针以及生物成像领域。
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