| In recent years, much attention has been paid to the design, syntheses, crystal structures and properties of coordination polymers. Besides the extensive application of nitrogen-containing heterocyclic ligands, such as 4,4'-bipyridine, aromatic carboxylic acids, owing to their unique characteristics, have also been used in the construction of coordination polymers. However, the methods usually used are conventional solution and hydro(solvo)thermal reaction methods. Rheological phase reaction method, as a new soft chemistry synthetic method put forward by our laboratory, has been successfully applied in the preparation of many functional materials, such as the positive and negative electrode materials of lithium ion secondary battery. This method has many advantages, for example, the reaction condition is mild, the reaction time is short and the operation is very simple. However, the researches on its application to the preparation of single crystals are still rare.In this research, valuable explorations about the application of rheological phase reaction method to the preparation of aromatic carboxylate single crystals were carried out. With zinc oxide or strontium chloride, lanthanide oxide or chloride, aromatic carboxylic acids (benzoic acid, salicylic acid, ct-furancarboxylic acid, a-thiophenecarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid) and 1,10-phenanthroline, a series of novel aromatic carboxylate complexes or coordination polymers were obtained through the molecular recognition and self-assembly of the reactants in the rheological phase system, which open a new way for this synthetic method and offer a new method for single crystal growth. Their crystal structures and spectral properties were characterized. The relationship between crystal structures and luminescent properties were discussed. The main results are as follows:1. An 1-D coordination polymer {[Tb(FUR)3(H2O)2]-DMF}n with intense green luminescence was synthesized, in which each Tb atom is eight-coordinated and the adjacent Tb atoms are linked into 1-D chains through bridging furancarboxylate ligands. The DMF molecules do not coordinate to the Tb atom and are linked to the 1-D chains through intermolecular hydrogen bonds. These 1-D chains are connected into 2-D layers through hydrogen bonds and π-π aromatic stacking interactions.2. A novel ionic dimer [Tb2(Hsal)8(H2O)2][(Hphen)2]-2H2O was synthesized from SrCh, TbCb, salicylic acid and 1,10-phenanthroline. During the experiment, it was found that the existence of Sr2+ plays a control role in the crystal growth. In this complex, the dimeric [Tb2(Hsal)8(H2O)2]2- anions are linked into 1-D chains by intermolecular hydrogen bonds. The mono-protonated [(Hphen)2]+ cations are located on the both sides of the 1-D chains. The π-π stacking interactions between the phen molecules and the benzene rings of salicylate ligands link the 1-D chains into 2-D layers. When irradiated by UV light, it emits intense green luminescence of Tb3+ ions, however, due to the energy mismatch, its luminescentIIIintensity is lower than that of the binary complex Tb(Hsal)3(H2O)2-2H2O.3. Two ionic dimeric complexes with novel crystal structures and strong red luminescence were obtained. It is worth to note that in [Eu2(Hsal)8][Zn(phen)3]-(H2salXH2O) (2-1), there are two independent dimeric [Eu2(Hsal)8]2" anions. Eul is eight-coordinated and Eu2 is in a nine-coordination environment. Weak intermolecular hydrogen bonds formed between the salicylate ligands and the lattice water molecules link the dimeric Eul anions into 1-D chains. In [Eu2(TPA)8][Zn(TPA)(phen)2]2-(H2O)2(2-2), the coordination environment of Eu3+ ion is the same as that of Eul in complex 2-1. While in these two complexes the coordination geometries around the Zn atoms are obviously different because of the different reaction conditions.4. Three Ln-Zn tetranuclear heterometallic complexes Tb2Zn2(Bzo)io(phen)2 (3-1), Tb2Zn2(TPA)io(phen)2 (3-2) and Eu2Zn2(Bzo)io(phen)2 (3-3) were synthesized and charact...
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