【作者】 冯维旭；

【导师】 吕兴强；

【作者基本信息】 西北大学 ， 应用化学， 2014， 博士

【摘要】 由于镧系金属离子如Nd3+, Yb3+以及Er3+等具有良好的近红外发光性能而在发光器件、光通讯以及荧光免疫分析等领域潜在的重要应用价值,近年来越来越受到人们的重视,成为材料领域的研究重点之一。但迫于镧系金属离子的f-f跃迁宇称禁阻,其自身摩尔吸光系数较低,使得设计合适的有机官能团(“天线效应”)来高效敏化发光成为一个重要的研究内容；此外,稀土化合物应用到实际发光材料中,还需要解决其机械强度差、热稳定性差以及分散不均匀等科学难题。本论文从提高基于含N202和0202结构的席呋碱-Zn(II)能量“给体”来敏化Ln3+离子(Nd3+, Yb3+及Er3+)的近红外发光的量子效率着手,系统研究了阴离子类型、反应摩尔比、溶剂和辅助配体的存在对Zn(Ⅱ)-Ln(Ⅲ)异金属配合物结构的自组装规律,探索出有高量子效率的反应控制条件；同时,通过烯丙基、苯乙烯基及噻吩基等功能性官能团的引入,以有优良近红外发光性能的含Salen类席呋碱的Zn-Ln目标化合物为结构基元,首次尝试了加成共聚或电化学均聚来制备Wolf Type Ⅱ类混金属聚合物材料的探索。一方面利用“能级匹配”原则成功地确定出量子效率接近1%的含Salen类席呋碱的Zn-Ln化合物结构基元的结构条件；并利用共价键键合的方法成功地开发出系列PMMA、PS及PVK等基质和聚噻吩类的Wolf Type Ⅱ混金属聚合物材料。具体内容如下：(1)基于含N202和0202结构的柔性环已烷连接基的Salen类席呋碱H2L1(N,N’-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine)的Zn2+及Ln3+的自组装规律在于：摩尔比1：1：1条件下,OAc-及N03-共存的醇溶剂体系易得到OAc-桥连Zn2+及九配位的Ln3+的异二核配合物：[Zn(OAc)Ln(L1)(NO3)2](Ln=Nd, Yb, Er或Gd, Ⅱ-2-5);溶剂体系引入DMF,可得到OAc-桥连Zn2+及十配位的Ln3+的异二核配合物[Zn(OAc)Ln(L’)(NO3)2DMF](Ln=Nd, Yb, Er或Gd, Ⅱ-6-9);溶剂体系引入MeCN,可得到得到Zn2+轴向为乙腈占据及十配位的Ln3+的异二核配合物[Zn(MeCN)Ln(L1)(NO3)3](Ln=Nd, Yb, Er或Gd,11-10-13).摩尔比2：2：1条件下,单独的OAc-或Cl-可分别得到了异三核配合物：[Zn2Ln(L1)2(OAc)3](Ln=Nd, Yb, Er或Gd,11-14-17)及[Zn2Ln(L1)2(Cl)3](Ln=Nd, Yb, Er或Gd,11-18-21); Cl-与N03-共存可自组装得到[Zn2Ln(L1)2(Cl)2(NO3)](Ln=Nd, Yb, Er或Gd,Ⅱ-22-25).光物理性质表明,异三核体系相对异二核体系,由于多个发光中心的存在而表现出更高量子效率的近红外发光性能；同时减少或避免Ln3+离子周围震荡基团的存在,化合物的近红外发光性能也得到了有效的提高。(2)基于含N202和0202结构的柔性环已烷连接基的Salen类席呋碱H2L1的ZnCl2及Ln(NO3)3的自组装,加入辅助第二配体邻香草醛(HL2), Ln(NO3)3的不同用量大小可分别得到异三核配合物：[ZnLn2(L1)2(L2)(NO3)2Cl](Ln=Nd, Yb, Er或Gd, Ⅲ-1-4)以及异二核[Zn(Cl)Ln(L1)(L2)(NO3)(MeCN)](Ln=Nd, Yb, Er或Gd, Ⅲ-5-8);基于含N202和0202结构的柔性环已烷连接基的Salen类席呋碱H2L1在有N03-存在的Zn2+及Ln3+的自组装中,辅助配体吡啶的引入,异二核配合物[Zn(Py)Ln(L1)(NO3)3](Ln=Nd, Yb, Er或Gd, Ⅲ-9-12)尤其能稳定存在。光物理性质结果表明：吡啶第二配体在Zn2+轴向占据的异二核化合物能表现出量子效率接近1%的近红外发光性能；结构特征在于柔性环已烷连接基的引入能实现1LC及3LC的双模式敏化,且Ln3+离子周围完全避免了震荡基团的存在。(3)结合(1)和(2)的研究结果,利用柔性环已烷连接基的引入及Zn2+轴向吡啶第二配体的存在的前提,先通过引入烯丙基官能团得到有双烯丙基端基的席呋碱碱配体H2L3(N,N’-bis(5-allyl-3-methoxysalicylidene)cyclohexane-1,2-diamine),近一步成功自组装得到[Zn(Py)Ln(L3)(NO3)3](Ln=La, Nd, Yb, Er或Gd, Ⅳ-1-5);用此系列有双烯丙基端基的异二核配合物为单体,尝试探索了其在助催化剂AIBN作用下与甲基丙烯酸甲酯(MMA)共聚合的研究。结果表明：异二核配合物单体的烯丙基因无法自由基聚合而得到了系列PMMA基的掺杂类杂化材料PMMA/[Zn(Py)Ln(L3)(NO3)3](Ln=La, Nd, Yb, Er或Gd,IV-6-12)。同时,考察了掺杂类杂化材料的热稳定性及光物理性能。(4)为改进(3)的不足,利用柔性环已烷连接基的引入及Zn2+轴向吡啶第二配体的存在的前提,通过苯乙烯基官能团的引入,合成得到有双苯乙烯基端基的席呋碱碱配体H2L4(N,N’-bis(5-phenylethylene-3-methoxysalicylidene)cyclohexane-1,2-diamine),再成功自组装得至[Zn(Py)Ln(L4)(NO3)3](Ln=La, Nd, Yb, Er或Gd,V-1-5)；利用此配合物为单体分别与MMA,苯乙烯(ST)以及N-乙烯基咔唑(NVK)共聚合,在助催化剂AIBN作用下成功实现了自由基共聚而得到了三个系列Wolf Type Ⅱ类含Zn2+-Ln3+的混金属聚合物材料Poly(MMA-co-[Zn(Py)Ln(L4)(NO3)3])(Ln=La, Nd, Yb, Er或Gd,V-6-12),Poly(ST-co-[Zn(Py)Ln(L4)(NO3)3])(Ln=La, Yb或Gd, V-13-15)以及Poly(NVK-co-[Zn(Py)Ln(L4)(NO3)3])(Ln=La, Yb或Gd,V-16-18)。同时,在考察了混金属聚合物杂化材料的热稳定性及光物理性能基础上,探索了Ln3+离子的浓度淬灭效应。(5)利用柔性环已烷连接基的引入及Zn2+轴向吡啶第二配体的存在的前提,进一步通过噻吩官能团的引入,合成得到有双噻吩端基的席呋碱配体H2L5(N,N’-bis(5-thienyl-3-methoxysalicylidene)cyclohexane-1,2-diamine),与Zn2+和Ln3+自组装反应得到[Zn(Py)Ln(L5)(NO3)3](Ln=La, Nd, Yb, Er或Gd, Ⅵ-1-5),同时,考察了其Ln3+离子的敏化发光及能量传递,为下一步电化学聚合合成金属聚合物做准备。更多还原

【Abstract】 The near-infrared (NIR) luminescent properties from series of lanthanide ions, such as Nd3+, Yb3+or Er3+and their potential applications in the organic light-emitting diodes (OLED), optical communications and bio-analysis become one of the focused areas in material science. However, due to the forbidden parity from f-f transitions, the low molar absorption coefficients need the necessary chromophores ("antenna effect") to sensitize the NIR luminescence of these Ln3+ions, indirectly. On the other hand, the problems to poor mechanical property, low stability and uneven dispersion in their practical use as the optical materials must be overcome.In this thesis, in order to improve the NIR quantum efficiency of these Ln3+ions sensitized by Zn2+-based complexes based on the Salen-type Schiff-base ligands with both N2O2and O2O2groups as the energy donors, the reaction control conditions on high NIR quantum efficiency for the hetero-nuclear complexes are explored by studying the affects of anions, the molar ratio of the reactions, solvents and the introduction of ancillary ligands. Moreover, with the target Zn-Ln structure units with two terminal allyl, phenylethenyl and thienyl functional groups as the monomers, the constructions of series of Wolf Type II Zn2+-Ln3+-containing metallopolymer materials are obtained through the addition copolymerization. On the one hand, depending on the rule of "energy level match", the structure factors on Zn-Ln structure units with the high quantum efficiency (about1%) are studied. Moreover, series of novel PMMA, PS and PVK-supported Wolf Type II metallopolymer hybrid materials are obtained through the covalent-bonding. The detailed content is shown as follows:(1) On the self-assembly of Zn2+and Ln3+with Salen-type Schiff-base ligand H2L1(N, N’-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) with both the inner cis-N2O2and the outer O2O2groups, the rules are summarized. When the reaction molar ratio of the ligand, Zn2+and Ln3+is1:1:1, the co-existence of OAc-and NOa-in alcohol-containing solvent systems, series of hetero-binuclear Zn-Ln complexes [Zn(OAc)Ln(L1)(NO3)2](Ln=Nd, Yb, Er or Gd, Ⅱ-2-5) with OAc-bridged between Zn2+and nine-coordinate Ln3+ion are obtained. While the further introduction of DMF, endows the obtainment of series of hetero-binuclear Zn-Ln complexes [Zn(OAc)Ln(L1)(NO3)2DMF](Ln=Nd, Yb, Er or Gd, Ⅱ-6-9) with OAc-bridged between Zn2+and ten-coordinate Ln3+ion. If the solvent of MeCN is used in the reaction systems, series of hetero-binuclear Zn-Ln complexes [Zn(MeCN)Ln(L1)(NO3)3](Ln=Nd, Yb, Er or Gd,11-10-13) are self-assembled, where the axial position of Zn2+is occupied by MeCN, and Ln3+are ten-coordinated from four O atoms of the O2O2moiety and six O atoms of three bidentate NO3-anions. On the other hand, under the condition of a molar ratio of2:2:1, the use of either OAc-or Cl-gives the similar series of hetero-trinuclear Zn2Ln complexes [Zn2Ln(L1)2(OAc)3](Ln=Nd, Yb, Er or Gd,11-14-17) or [Zn2Ln(L1)2(Cl)3](Ln=Nd, Yb, Er or Gd,11-18-21), respectively. Moreover, the co-existence of Cl" and NO3" also endows the obtainment of the similar series of hetero-trinuclear Zj^Ln complexes [Zn2Ln(L1)2(Cl)2(NO3)](Ln=Nd, Yb, Er or Gd,11-22-25). The results of their photophysical properties show that the hetero-trinuclear complexes exhibit relatively higher NIR quantum efficiency in comparison with the hetero-binuclear complexes, because of the plurality of more energy donors besides the reduction or avoidance of the quenching effect.(2) The further introduction of o-vanillin (HL2) as the ancillary ligand in self-assembly of ZnCl2and Ln(NO3)3with Salen-type Schiff base ligand H2L1, two series of hetero-trinuclear complexes [Zn(Cl)Ln2(L1)2(L2)(NO3)2](Ln=Nd, Yb, Er or Gd, Ⅲ-1-4) and [Zn(Cl)Ln(L1)(L2)(NO3)(MeCN)](Ln=Nd, Yb, Er or Gd, Ⅲ-5-8) are obtained by changing the molar amounts of Ln(NO3)3. If with pyridine as the ancillary ligand, hetero-nuclear complexes [Zn(Py)Ln(L1)(NO3)3](Ln=Nd, Yb, Er or Gd, Ⅲ-9-12) could be obtained, and the expected NIR quantum efficiency (about1%) is shown from the energy transfer of both the3LC and1LC of the ligands.(3) Ruled by the achievement from points (1) and (2), the introduction of two terminal allyl functional groups on the flexible Salen-type Schiff-base ligand for H2L3(N,N’-bis(5-allyl-3-methoxysalicylidene)cyclohexane-1,2-diamine), gives the products of [Zn(Py)Ln(L3)(NO3)3](Ln=La, Nd, Yb, Er or Gd, Ⅳ-1-5) complexes. Although the copolymerization with methyl methacrylate (MMA) in the presence of co-catalyst AIBN is expected, the doped hybrid materials PMMA/[Zn(Py)Ln(L3)(NO3)3])(Ln=La, Nd, Yb, Er or Gd, Ⅳ-6-12) are obtained due to the failure of radical polymerization between the terminal ally groups with MMA. Meanwhile, the thermal stability and photophysical properties of the doped hybrid materials are studied.(4) In order to overcome the limit of point (3), the new flexible Salen-type Schiff-base ligand H2L4(N,N’-bis(5-phenylethylene-3-methoxysalicylidene)cyclohexane-1,2-diamine) with two terminal phenylethylene functional groups is designed. With the obtained complexes [Zn(Py)Ln(L4)(NO3)3](Ln=La, Nd, Yb, Er or Gd, V-1-5) as the monomers, through the radical copolymerization with MMA, ST or NVK in the presence of co-catalyst AIBN, three series of Wolf Type Ⅱ metallopolymers Poly(MMA-Co-[Zn(Py)Ln(L4)(NO3)3])(Ln=La, Nd, Yb, Er or Gd, V-6-12), Poly(ST-Co-[Zn(Py)Ln(L4)(NO3)3])(Ln=La, Yb or Gd, V-13-15) and (Ln=Poly(NVK-Co-[Zn(Py)Ln(L4)(NO3)3])(Ln=La, Nd, Yb, Er or Gd, V-16-18) are successfully obtained, respectively. Also besides the check of thermal stabilities and photophysical properties, the Ln3+-based concentration quenching effect are studied, especially.(5) Through the modification of thiophene functional groups to the flexible Schiff base ligand for H2L5(N,N’-bis(5-thienyl-3-methoxysalicylidene)cyclohexane-1,2-diamine), its self-assembly with the new ligand with Zn3+, Ln3+and pyridine (Py), endows the obtainment of series of hetero-binuclear [Zn(Py)Ln(L5)(NO3)3](Ln=Nd, Yb, Er, Gd, Ⅵ-1-4). Moreover, the energy transfer and the sensitization of NIR luminescence of Ln3+ions are discussed, and their use for obtaining the conductive Zn2+-Ln3+-containing Wolf Type Ⅱ metallopolymers by electrochemical self-polymerization will be finished in the future.更多还原