| Due to its special optical, electrical and magnetic properties, rare earth-based organic-inorganic functionalized complexes have become a hot issue in the research field of coordination chemistry, material science, etc. Design and synthesis of a good organic ligand is the key factor to the research on rare earth compounds, which is also a major determinant for its structure and properties. Open-chain crown ethers can improve effectively complexation activity and selectivity of metal ions by changing the terminal groups, and this is of great significance in the design and synthesis of the functionalized rare earth complexes with novel structure and good luminescent performance. Open-chain crown ethers with amide-type end group has been deeply studied and widely applied because of its strong bonding ability, easy cyclization and high-coordination selectivity, etc. For these reasons, amide-based open-chain crown ether ligands are very good chelating ligand for rare earth ions, and its rare earth complexes as well as their 3d-4f heterodinuclear complexes are expected to be applied in organic light-emitting materials, fluorescence immunoassay, fluorescence probe, etc.In our presention, six novel open-chain crown ether ligands are synthesized, together with their rare earth complexes. 12 single crystals were obtained. We studied the effect of both terminal group of ether chain and substituted group of fluorophore on structure and luminescence properties of targeted complexes. More deatials are as follows:1. The background of this paper as well as the characteristics and applications for rare earth complexes are briefly overviewed. The research progresses on rare earth nitrate coordination compounds constructed by amide-based open-chain crown ether ligands was emphasised in the end of this part.2. The amide-based open-chain crown ethers ligands L1 and L2 based on 2, 3-dihydroxynaphthalene with different terminal amide groups were synthesized, together with their homo rare earth nitrate complexes and 3d-4f heteronuclear complexes. The crystal structures and lunminescence properties of resulted complexes are studied. The ligands L1 and L2 and their complexes are listed as follows: L1: 2-{1-[(Bis-pyridin-2-ylmethyl-amino)-methyl]-3-[(diisopropylcarbamyl)-methoxy]-naphthalen-2-yloxy}-N,N′-diisopropyl-acetamide L2: N-{2-{1-[(bis-pyridin-2-ylmethyl-amino)-methyl]-3-[(4-methyl-piperidyl-carbamyl)-methoxy]-naphthalen-2-yloxy}-acetyl-}-4-methyl-piperidine Ln L1(NO3)5(Ln=Nd(III), Eu(III), Gd(III), Tb(III)); [Nd2Zn2L1(NO3)10·(H2O)2]·4C2H3N· C3H7 NO, [Ln Zn L1(NO3)5·H2O]·3C2H3N(Ln=Eu(III), Gd(III), Tb(III)); [Ln Zn L2(NO3)4· 2H2O]·NO3(Ln=Eu(III), Tb(III))3. A new type of ligand L3 of amide-based open-chain crown ethers based on benzene ring containing DPA as a recognizing group is synthesized with 3,4-dihydroxybenzaldehyde. The homo rare earth nitrate complexes as well as 3d-4f analogues are synthesized. The crystal structures and luminescence properties are studies in detail. The ligand L3 and its complexesare listed as follows: L3:3-{1-[(Bis-pyridin-2-ylmethyl-amino)-methyl]-4-[(4-methyl-piperidyl-carbamyl)-meth oxy]-benzene-2-yloxy}-N,N′-diisopropyl-acetamide [Ln4L3(NO3)12]·2C4H8O2(Ln=Eu(III), Tb(III)); [Ln2Zn2L3(NO3)10]·2C2H3N·C4H8O2(Ln= Eu(III), Tb(III)), [Ln Cd L3(NO3)5]·4C2H3N(Ln=Eu(III), Tb(III))4. The amide-based open-chain crown ethers ligands L~L based on benzene ring with different-substitution groups and their rare earth nitrate complexes are synthesized for the purpose of studying effect of the substituted group of fluorophore on structure and luminescence properties of targeted complexes. The ligand L4~L6 and their complexes are listed as follows: L4: 2,2′-(4-formyl-benzene-3,4-dioxyl)-bis(N,N′-diisopropyl(acetamide)) L5: 2,2′-(4-bromine-benzene-3,4-dioxyl)-bis(N,N′-diisopropyl(acetamide)) L6: 2,2′-(4-tertbutyl-benzene-3,4-dioxyl)-bis(N,N′-diisopropyl(acetamide)) Ln L(NO3)5(Ln=Eu(III), Gd(III), Tb(III); L=L4, L5, L6)... |
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