CN104447876A - 一种铂(ii)炔类配合物及应用 - Google Patents
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- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 52
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 9
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 4
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- 229910052700 potassium Inorganic materials 0.000 abstract description 4
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- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 abstract 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 23
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
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- 125000000304 alkynyl group Chemical group 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
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- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
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- QUNYZQOYKBJCST-UHFFFAOYSA-N cyclopenta-1,3-diene 5-ethynylcyclopenta-1,3-diene ruthenium(2+) Chemical compound [Ru++].c1cc[cH-]c1.C#C[c-]1cccc1 QUNYZQOYKBJCST-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical compound P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3611—Organic materials containing Nitrogen
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
本发明提供一种铂(II)炔配合物及其应用。其结构是以联二吡啶衍生物为配体的铂(II)炔萘酰亚胺类化合物。其制备方法为首先将氯亚铂酸钾和二甲基亚砜反应,得到铂氯二甲亚砜配合物,然后再与联二吡啶配体反应得到联二吡啶铂(II)氯配合物,最后与炔配体发生Sonogashira反应得到一系列联二吡啶铂(II)炔萘酰亚胺类化合物。本发明合成出的铂配合物经测试结果表明具有强的光限幅性能,此类化合物能够在非线性吸收材料中得到应用。
Description
技术领域
本发明涉及有机光电材料领域,尤其涉及非线性光学材料,含有新型有机铂(II)炔配合物的非线性光学材料。
技术背景
当今信息时代,随着信息产业的快速发展,对于信息技术、信号处理技术等提出了更高的要求,相应地对光学材料也提出了更高要求,因而具有特殊信息处理功能和超快响应的光电材料将成为信息材料发展的主体。对于光电子技术的发展,非线性光学起到了关键的作用。由于非线性光学材料在光信息处理、光计算、光开关及光限幅等领域具有重要的作用和应用前景,已成为近年来的研究热点。
非线性光学材料的发展一直以强的非线性响应、高的非线性光学系数、好的环境稳定性和高品质的材料性能为目标,在无机晶体、非晶材料和有机高分子等领域都取得了重大进展。由于单一的无机材料或有机材料都存在自身不可克服的缺点,而金属有机配合物因其兼具无机和有机材料的优点,具有很广阔的发展前景,成为目前非线性光学材料研发的主流趋势之一。
金属配合物具有较大的基态偶极距和极化率,以及较低的激发态能级,有利于提高材料的光电响应速度。同时金属原子(离子)的介入,可引起更多的能级参与杂化,影响金属配合物的双光子吸收性质。此外金属与配体之间的相互作用可使分子内的电荷分布发生畸变,增大分子内的电荷转移程度,从而有利于优化非线性光学活性。目前对该类金属有机配合物的研究主要集中在金属酞菁类配合物(J Phys Chem A,1993,97(41):10515-10517;Chem Phys,2002,279(2-3):209-213),二茂铁类化合物(Inorg Chem,2003,42(3):913-920)和铂配 合物(Top.Curr.Chem.2007,281,205-268)等领域。其中铂炔配合物,由于其优秀的光物理性质,长期以来受各国科研人员的持续关注与深入研究。
1996年,Sato等报道了铂膦配合物与乙炔基二茂钌合成得到含膦配体的铂炔配合物(Organomet Chem,1996,508(1-2):159-167)。2001年,Peter等人合成了一系列铂桥联的四乙炔基乙烯低聚物,该类化合物具有很强的MLCT(金属到配体的电荷转移),其二阶非线性极化率随聚合单体的增加而增大(Organomet Chem,1996,508(1-2):159-167)。2005年Sun报道了一系列三联吡啶铂芳炔配合物的合成及其光限幅性能,当炔配体上带有供电子取代基时,配合物的荧光量子效率较低,且无三重态吸收。该类配合物对532nm脉冲激光(4.1ns)具有显著的光限幅性能,可作为潜在的光限幅材料(Inorg.Chem.2005,44,4055-4065)。2009年,Zieba等将带有烷氧硅基的双三丁基膦铂苯撑乙炔撑配合物通过凝胶过程进行杂化,制得在可见光区具有宽幅非线性吸收的功能杂化玻璃材料(Adv.Func.Mater.2009,19,235-24)。2010年,赵建章课题组报道了一种联二吡啶铂炔萘酰亚胺化合物(结构式I),通过在炔基引入萘酰亚胺,增加激发态寿命,用来做上转换材料(Dalton Transactions 2010,135,2832-2840)。2012年Sun等报道了一系列铂炔类化合物(结构式II),在炔基一侧通过增加共轭长度来延长分子的激发态寿命,用于非线性吸收材料(Dalton Transactions 2012,40,12353-12357;U.S.Patent 2012/0100628A1.2012-4-26)。2014年Liu Rui通过在联二吡啶铂炔两侧引入大的共轭基团,设计合成了一系列铂炔类化合物(结构式III),研究了结构变化对于化合物发光性能的影响,经测试表明此类化合物具有很好的反饱和吸收性能(Inorganic Chemistry 2014,53,9516-9530)。总之,联二吡啶铂炔配合物作为光限幅材料具有非线性光学系数大、激光损伤阈值高、光学响应时间短、结构易修饰、光物理性质可调控以及可与其他材料进行杂化组合,具有广阔的 应用前景。其中在近几年的报道中萘酰亚胺结构由于其具有较大的共轭体系以及长的激发态寿命等优良的光物理性质,引起了科研人员的重视,将其引入到联二吡啶铂炔配合物中尤其值得关注。
在上述含有萘酰亚胺结构的联二吡啶铂炔配合物中,萘酰亚胺结构大都通过连接基与炔基相连。此外尽管有与铂直接相连的化合物报道,但没有同时对 联二吡啶一侧进行修饰。为此我们在炔基直接与萘酰亚胺结构相连接,同时在联二吡啶一侧引入芴、咔唑等芳香基团构建联二吡啶配体,设计制备了基于这两种配体的一类新型铂炔配合物,其瞬态吸收、反饱和吸收以及非线性透过率试验表明,该类化合物具有较好的光物理性质,其光限幅性能比之前报道类似化合物更好,可作非线性吸收材料应用。
发明内容
本发明的目的在于提出一类具有优良非线性吸收性能的铂(II)炔类配合物以及其应用。
本发明首先设计合成一系列联二吡啶铂(II)炔配合物,通过在联二吡啶一侧引入芴、咔唑等芳香类基团,来增大配合物的共轭体系构建联二吡啶配体。在炔基一侧通过引入萘酰亚胺基团。这样由这两种配体合成得到铂(II)炔类配合物,能提高分子的激发态寿命,达到改善其光限幅性能的目的。
本发明中,首先将氯亚铂酸钾与二甲基亚砜反应,得到铂(II)氯二甲亚砜配合物,然后再与联二吡啶配体反应得到联二吡啶铂(II)氯配合物(2),最后与炔配体发生Sonogashira反应得到一系列联二吡啶铂(II)炔萘酰亚胺类配合物。收率在51.3-58.2%,反应式如下所示,
其中R1为下述基团中一种:
其中,R’、R”、R”’是H,碳原子数1至8的烷基。
附图说明
图1化合物T1-T4氢谱
图2化合物T1、T2、T4碳谱
图3T1-T4在二氯甲烷溶液中的紫外-可见吸收光谱(c=1.0×10-5molL-1)
图4归一化的T1-T4在二氯甲烷溶液中的荧光发射光谱(c=1.0×10-5molL-1)
图5为T1-T4在甲苯溶液中的瞬态吸收光谱
图6为T1-T4在甲苯溶液中532nm下测得的透过率-入射光密度曲线。
具体实施方式
以下具体实施例用来进一步说明本发明。
合成实施例
实施例1:芴-联二吡啶铂(II)氯配合物(化合物M-1)的合成
反应式:
向250mL的三口烧瓶中加入(224mg,0.534mmol)的铂(II)氯二甲亚砜配合物2和(438mg,0.534mmol)的4,4′-双(9,9-二己基芴基)联二吡啶(化合物C-1),再分别加入60mL乙腈和100mL二氯甲烷。加热回流6-8小时,反应结束后降至室温,减压旋去溶剂。得到的粗产品通过柱层析纯化,展开剂为二氯甲烷。得到290mg黄色固体,收率为87.2%。1H NMR(400MHz,CDCl3):δ9.73(m,2H),8.22(s,2H),7.83(d,J=7.8Hz,2H),7.73(d,J=2.5Hz,6H),7.64(s,2H),7.33(m,6H),2.01-1.97(m,8H),1.05-0.96(m,24H),0.67(t,J=6.9Hz,12H,),0.60-0.56(m,8H)。13C NMR(400MHz,CDCl3)δ(ppm):153.8,150.5,148.3,147.8,143.1,141.0,130.1,129.6,128.9,128.4,126.7,124.3,123.2,121.6,118.7,53.2,43.9,31.8,29.9,24.6,22.8,14.2.Elemental analysis calcd.(%)for C60H72Cl2N2Pt:C,66.27;H,6.61;N,2.61.found C,66.28;H,6.67;N,2.58。
实施例2:化合物T-1的合成
反应式:
向250mL的三口烧瓶中加入(145mg,0.134mmol)的化合物M-1,(92mg, 0.333mmol)的N-丁基-6-乙炔基萘酰亚胺(化合物N-Bu-NI≡)和(6mg,0.003mmol)的碘化亚铜,再分别加入50mL无水二异丙胺和90mL无水二氯甲烷。在氮气保护下加热回流20-24小时,反应结束后降至室温,减压旋去溶剂。得到的粗产品通过柱层析纯化,展开剂为二氯甲烷∶石油醚=1∶1。得到122mg红色固体,收率为58.2%。1H NMR(400MHz,CDCl3):δppm 9.87(d,J=5.9Hz,2H),9.21(d,J=8.3Hz,2H),8.58-8.49(m,6H),8.00-7.75(m,12H),7.56(t,J=7.8Hz,2H),7.43(d,J=2.9Hz,6H),4.21(t,J=7.6Hz,4H),2.09-2.05(dd,J=10.7Hz,J=5.4Hz,8H),1.79-1.72(m,4H),1.53-1.43(m,4H),1.15-1.04(m,24H),1.22(t,J=7.3Hz,6H),0.76(t,J=7.0Hz,12H),0.69-0.66(m,8H).13C NMR(400MHz,CDCl3):δppm 164.42,164.14,156.51,152.58,152.16,151.54,151.23,144.47,139.55,134.23,134.03,133.01,132.97,131.19,130.80,130.03,128.56,128.37,127.35,126.51,126.42,125.42,123.16,122.78,121.35,120.86,120.53,120.39,119.42,101.81,100.32,55.57,40.33,40.27,31.54,30.31,29.78,23.89,22.63,20.41,14.02,13.97.Elemental analysis calcd.(%)for C96H100N4O4Pt:C,73.45;H,6.41;N,3.53.found C,73.49;H,6.42;N,3.57。
实施例3:咔唑-联二吡啶铂(II)氯配合物(化合物M-2)的合成
反应式:
过程同于实施例1,只是将反应物C-1换为4,4′-双(N-己基咔唑基)联二吡 啶(化合物C-2)。
得到的粗产品通过柱层析纯化,展开剂为二氯甲烷。得到黄色固体,收率为91.2%。1H NMR(400MHz,CDCl3):δ8.91(s,2H),8.82-8.81(d,J=5.0Hz,2H),8.58(s,2H),8.24-8.22(d,J=3.8Hz,2H),7.94-7.91(dd,J=4.3Hz,2H),7.72-7.70(dd,J=2.5Hz,2H),7.54-7.43(m,6H),7.33-7.29(t,J=3.7Hz,2H),4.33-4.29(t,J=4.0Hz,4H),1.93-1.86(m,4H),1.41-1.28(m,12H),1.07-1.05(m,16H),0.91-0.87(t,J=3.4Hz,12H).13C NMR(400MHz,CDCl3):156.82,150.21,149.60,141.01,140.97,128.90,126.11,124.95,123.50,122.95,121.61,119.31,119.25,119.10,109.16,109.02,43.27,31.61,29.00,27.01,22.60,14.08.Elemental analysis calcd.(%)for C46H46Cl2N4Pt:C,60.13;H,5.21;N,6.02.;found C,60.18;H,5.23;N,6.06。
实施例4:化合物T-2的合成
反应式:
过程同于实施例2,只是将反应物M-1换为化合物M-2。
得到的粗产品通过柱层析纯化,展开剂为二氯甲烷。得到暗红固体,收率为51.3%。1H NMR(400MHz,CDCl3):δppm 8.21-7.94(m,6H),7.60-7.31(m,6H),7.11-6.90(m,8H),6.70-6.36(m,10H),3.65(s,8H),1.51-1.37(m,12H),1.26(s,12H),0.99(t,J=7.2Hz,6H),0.89(t,J=6.2Hz,6H).13C NMR(400MHz,CDCl3): δppm 163.25,162.91,156.18,149.72,148.54,140.62,139.83,131.97,131.56,129.54,129.02,128.67,127.19,126.14,124.95,124.33,123.13,122.64,121.62,121.16,120.57,119.34,119.17,118.02,117.83,108.41,42.85,39.98,31.49,30.27,28.66,26.93,22.61,20.52.14.12,13.95.Elemental analysis calcd.(%)for C82H74N6O4Pt:C,70.20;H,5.34;N,5.97.found C,70.22;H,5.32;N,5.99。
实施例5:双芴-联二吡啶铂(II)氯配合物(化合物M-3)的合成
反应式:
过程同于实施例1,只是将反应物C-1换为化合物C-3。反应时间延长至10小时。
得到的粗产品通过柱层析纯化,展开剂为二氯甲烷∶石油醚=1∶1。得到黄色固体,收率为89.8%。1H NMR(400MHz,CDCl3):δppm 8.83-8.82(m,4H),7.89-7.64(m,22H),7.39-7.30(m,6H),2.15-2.11(m,8H),2.06-2.02(m,8H),1.14-1.09(m,48H),0.79-0.65(m,40H).13C NMR(400MHz,CDCl3):δppm156.92,152.02,151.96,151.53,151.03,149.97,149.68,142.03,141.14,140.77,140.48,140.37,139.56,137.02,132.35,132.24,131.58,131.55,128.60,128.47,127.07,126.83,126.37,126.29,126.10,122.95,121.88,121.53,121.46,120.33,120.30,119.94,119.77,119.28,55.54,55.20,40.40,31.50,29.72,29.68,23.84,23.80, 22.59,14.04.Elemental analysis calcd.(%)for C110H136Cl2N2Pt:C,75.33;H,7.79;N,1.62.found C,75.40;H,7.82;N,1.60。
实施例6:化合物T-3的合成
反应式:
过程同于实施例2,只是将反应物M-1换为化合物M-3。
得到的粗产品通过柱层析纯化,展开剂为二氯甲烷。得到红色固体,收率为57.4%。1H NMR(400MHz,CDCl3):δppm 9.85(d,2H),9.21(dd,2H),8.58-8.48(m,6H),7.97-7.62(m,24H),7.56-7.48(m,2H),7.38-7.31(m,6H),4.18(t,4H),2.16-2.01(m,20H),1.77-1.60(m,8H),1.49-1.41(m,8H),1.29-1.22(m,26H),1.15-1.08(m,10H),0.78-0.70(t,48H).13C NMR(400MHz,CDCl3):δppm 164.5,164.1,156.92,152.02,151.96,151.53,151.03,149.97,149.68,144.3,142.03,141.14,140.77,140.48,140.37,139.56,137.02,132.35,132.24,131.58,131.55,130.8,130.0,128.60,128.47,127.07,126.83,126.37,126.29,126.10,122.95,121.88,121.53,121.46,120.33,120.30,119.94,119.77,119.28,101.8,100.3,55.54,55.20,40.40,31.50,29.72,29.68,23.84,23.80,22.59,14.04,13.91.Elemental analysis calcd.(%)for C146H164N4O4Pt:C,78.53;H,7.37;N,2.49.found C,78.50;H,7.40;N,2.51。
实施例7:咔唑芴-联二吡啶铂(II)氯配合物(化合物M-4)的合成
反应式:
过程同于实施例1,只是将反应物C-1换为化合物C-4。反应时间为10小时。
得到的粗产品通过柱层析纯化,展开剂为二氯甲烷。得到黄色固体,收率为69.5%。1H NMR(400MHz,CDCl3):δppm 8.83-8.82(d,J=4.92,4H),8.40(S,2H),8.23-8.20(d,J=7.68,2H),7.87-7.80(m,10H),7.75-7.68(m,6H),7.51-7.43(m,6H),7.28-7.23(m,2H),4.35-4.32(t,J=7.08, 4H),2.15-2.12(m,8H),1.94-1.87(m,4H),1.42-1.27(m,14H),1.16-1.10(m,14H),0.89-0.86(t,J=6.82,6H),0.79-0.75(t,J=6.76,18H)13C NMR(400MHz,CDCl3):δppm 156.92,151.96,150.04,149.68,142.27,141.70,140.97,140.00,138.83,136.78,132.64,126.33,125.86,125.32,123.44,123.01,121.88,121.71,121.42,120.52,120.38,120.19,119.28,118.94,118.92,108.97,108.90,55.53,43.27,40.55,31.65,31.54,29.76,29.04,27.04,23.88,22.64,22.60,14.07.Elemental analysis calcd.(%)for C96H110Cl2N4Pt:C,72.73;H,6.95;N,3.57.found C,72.70;H,6.99;N,3.53。
实施例8:化合物T-4的合成
反应式:
过程同于实施例2,只是将反应物M-1换为化合物M-4。
得到的粗产品通过柱层析纯化,展开剂为二氯甲烷∶石油醚=1∶1。得到红色固体,收率为56.1%。1H NMR(400MHz,CDCl3):δppm 9.70(d,J=5.8,2H),9.19(d,J=8.4,2H),8.56-8.51(m,6H),8.39(s,2H),8.21(d,J=7.7,2H),7.94-7.73(m,18H),7.55-7.43(m,8H),7.28-7.25(m,2H),4.35(t,J=7.0,4H),4.18(t,J=7.4,4H),2.20-2.08(m,8H),1.95-1.87(m,4H),1.77-1.69(m,4H),1.50-1.25(m,20H),1.15-1.20(m,24H),0.98(t,J=7.3,6H),0.88(t,J=6.9,6H),0.77-0.69(m,18H). 13C NMR(400MHz,CDCl3):δppm 164.52,164.23,156.51,152.87,152.62,152.04,151.57,144.41,142.73,140.90,140.31,137.95,134.12,134.09,133.05,132.94,132.13,131.16,130,97,130.04,128.38,126.66,126.51,126.02,125.13,123.56,122.97,122.7,121.86,121.33,120.94,120.86,120.51,120.22,119.48,119.04,118.98,109.03,108.97,101.93,100.31,55.72,43.37,40.53,40.27,31.60,31.59,31.02,3035,29.72,29.03,27.03,23.91,22.67,22.55,20.59,14.10,13.98.Elemental analysis calcd.(%)for C132H138N6O4Pt:C,76.71;H,6.75;N,4.03.found C,76.68;H,6.73;N,4.06。
测试实施例
实施例9:化合物T1-T4紫外-可见吸收光谱测试
以二氯甲烷为溶剂,将化合物T1-T4配成浓度为1×10-5mol/L的溶液。在室温条件下,持续通氮气30分钟后,使用Agilent8453型紫外可见光光度计,用1cm的石英比色皿,在200-800nm波段进行紫外吸收光谱扫描,测量化合物T1-T4在二氯甲烷溶液中的的最大吸收波长及摩尔吸光系数,测试结果见图3。
实施例10:化合物T1-T4荧光发射光谱测试
以二氯甲烷为溶剂,将化合物T1-T4配成浓度为1×10-5mol/L的溶液。在室温条件下,持续通氮气30分钟后,用1cm的石英比色皿,狭缝宽度为Iex/Iem=10nm/5nm进行分子荧光发射光谱扫描,测量化合物T1-T4在正己烷溶液中的相对荧光强度If,测试结果见图4。
实施例11:化合物T1-T4瞬态吸收光谱测试
以甲苯为溶剂,将化合物T1-T4配成浓度为1×10-4mol/L的溶液。在室温条件下,持续通氮气30分钟后,用瞬态吸收光谱仪测试化合物的瞬态吸收光谱。四个化合物在500nm至700nm均有强的并且正的吸收带,说明两个化合物在此波长范围内的激发态吸收截面要大于基态吸收截面。并且此吸收带是一个大而宽的峰型,可以把其激发态性质归属于电荷转移吸收,测试结果见图5。
实施例12:化合物T1-T4透过率-入射光密度曲线测试
以甲苯为溶剂,将化合物T1-T4配成浓度为1×10-4mol/L的溶液,通过激光激发制作了化合物的透过率-入射光密度曲线。在没有激光激发下,化合物T1-T4在甲苯溶液中达到80%的线性透过率,随着入射光密度的逐渐增加,四个化合物的透过率呈明显的下降趋势,最后线性透过率降低了65%,说明四个化合物具有良好的反饱和吸收性质,测试结果见图6。
表1列出了化合物T1-T4的光谱数据。图3中,化合物T1-T4的紫外吸收 波长在250nm,300nm,340nm,420nm处均有吸收,这些吸收峰归属于配体中心π-π*的跃迁。由图4看出,四个化合物最大荧光发射光谱位于627-629nm之间,均产生了较大的Stoke位移并且展现了较长的激发态寿命。由图5瞬态吸收测试光谱可以看出四个化合物激发态吸收截面要大于基态吸收截面,表明此类化合物可以作为反饱和吸收材料。图6透过率-入射光密度曲线看出随着入射光密度的逐渐增加,化合物的透过率呈明显的下降趋势,说明四个化合物具有良好的反饱和吸收性质。所有的数据表明,此类化合物均有强的光限幅性能,是一种较好的非线性光学材料。
表1化合物T1-T4的光谱性质
任何本领域的技术人员,在不脱离本发明的精神和范围的情况下,应当可以作出各种修改与变更。因此本发明的保护范围应当视为所附的权利要求书所限定的范围。
Claims (2)
1.一种铂(II)炔配合物,其特征在于,该化合物是以联二吡啶衍生物为配体的铂(II)炔萘酰亚胺类配合物,其结构式如下:
其中R1为下述基团中一种:
其中,R’、R”、R”’是H,碳原子数1至8的烷基。
2.一种在非线性器件中材料的应用,其至少包括如权利要求1中的以联二吡啶衍生物为配体的铂(II)炔萘酰亚胺类配合物。
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