Near-Infrared Luminescent PMMA-Supported Metallopolymers Based on Zn鈥揘d Schiff-Base Complexes

详细信息    查看全文

• 作者：Zhao Zhang ; Weixu Feng ; Peiyang Su ; Xingqiang L眉 ; Jirong Song ; Daidi Fan ; Wai-Kwok Wong ; Richard A. Jones ; Chengyong Su
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：June 16, 2014
• 年：2014
• 卷：53
• 期：12
• 页码：5950-5960
• 全文大小：541K
• 年卷期：v.53,no.12(June 16, 2014)
• ISSN：1520-510X

文摘

On the basis of self-assembly from the divinylphenyl-modified Salen-type Schiff-base ligands H₂L¹ (N,N鈥?bis(5-(3鈥?vinylphenyl)-3-methoxy-salicylidene)ethylene-1,2-diamine) or H₂L² (N,N鈥?bis(5-(3鈥?vinylphenyl)-3-methoxy-salicylidene)phenylene-1,2-diamine) with Zn(OAc)₂路2H₂O and Ln(NO₃)₃路6H₂O in the presence of pyridine (Py), two series of heterobinuclear Zn鈥揕n complexes [Zn(Lⁿ)(Py)Ln(NO₃)₃] (n = 1, Ln = La, 1; Ln = Nd, 2; or Ln = Gd, 3 and n = 2, Ln = La, 4; Ln = Nd, 5; or Ln = Gd, 6) are obtained, respectively. Further, through the physical doping and the controlled copolymerization with methyl methacrylate (MMA), two kinds of PMMA-supported hybrid materials, doped PMMA/[Zn(Lⁿ)(Py)Ln(NO₃)₃] and Wolf Type II Zn²⁺鈥揕n³⁺-containing metallopolymers Poly(MMA-co-[Zn(Lⁿ)(Py)Ln(NO₃)₃]), are obtained, respectively. The result of their solid photophysical properties shows the strong and characteristic near-infrared (NIR) luminescent Nd³⁺-centered emissions for both PMMA/[Zn(Lⁿ)(Py)Nd(NO₃)₃] and Poly(MMA-co-[Zn(Lⁿ)(Py)Nd(NO₃)₃]), where ethylene-linked hybrid materials endow relatively higher intrinsic quantum yields due to the sensitization from both ¹LC and ³LC of the chromorphore than those from only ¹LC in phenylene-linked hybrid materials, and the concentration self-quenching of Nd³⁺-based NIR luminescence could be effectively prevented for the copolymerized hybrid materials in comparison with the doped hybrid materials.