| This paper summarizes the hydrothermal/solvothermal synthesis of compounds based on the flexible ligand as 1-hydroxyethane-1,1-diyldiphosphonic acid (H5L), under the effect of different N- heterocyclic amines templates. We have obtained ten new structural compounds (1)～(10), the crystal structures have been determined by IR, XRD, single crystal X-ray diffraction, and elementary analysis. Their thermal stabilities and fluorescence propertiies are studied. Here, we represent ten new compounds as:(1) [Zn(H3L)(Phen)]; (2) [Zn3(H2L)2(Phen)2]·2H2O(3) [Zn(H3L)(Bipy)]; (4) [Zn(H3L)(Phen)]·H2O(5) [Cd(H3L)(Phen)(H2O)]; (6) [Zn(H3L)(Bipy)]·H2O(7) [Zk1.5(H2L)(Bipy)(H2O)]·3H2O; (8) [Zn(H3L)(Phen)]·0.5(HOCH2CH2OH)(9) [Cu2(Phen)2(H2O)4]·(SO4)2; (10) [BTC-H3pytpy]·0.5H2OAbbreviation of ligands and N- heterocyclic amines: H5L(HEDP)=1-hydroxyethane-1,1-diyldiphosphonic acid [H3CCOH(PO3H2)2], H3BTC=1,3,5-benzenetricarboxylic acid, Phen=1,10-phenanthroline, Bipy=2,2’-Bipyridine, Pytpy=4’-(4-pyridyl)-2,2’:6’,2"-terpyridine.Single-crystal X-ray diffraction and fluorescence analysis reveals:Compound (1) has a one-dimensional zigzag-chain structure constructed from the asymmetric [ZnN2O3] units. The maximum of the fluorescent emission bands of (1) is located at 391 nm (λex=336 nm), it is extremely rare in compounds with close related structures. This unusual fluorescence would be further studied in optical areas.The asymmetric unit of compound (2) contains three Zn(Ⅱ) nucleus with four-, five- and six-coordination, respecsively. Kinds of coordination modes in structure have been rarely reported. Compound (2) displays two strong fluorescent emission bands which are located at 371 nm and 390 nm, and a weak fluorescent emission band at 412 nm (λex=336 nm).Compounds (3), (4), (6) and (8) are all have a zero-dimensional structure, the asymmetric unit contains one Zn(Ⅱ) nucleus with a common five-coordination, respecsively. The fluorescent emission bands of (3) is located at 371 nm (λex= 326 nm), which is particularly strong. Three maximum of the fluorescent emission bands of (4) with similar intensity are located at 380 nm,398nm and 420 nm (λex=255 nm). The maximal fluorescent emission bands of (6) is located at 360 nm (λex=275 nm). Fluorescent emission bands of (8) are located at 370 nm,390 nm and 412 nm (λex= 336 nm).Compound (5) has a zero-dimensional structure, and the central Cd(Ⅱ) ion is in six coordination environment. Four maximal fluorescent emission bands of (5) with similar intensity are located at 383 nm,395 nm,399 nm and 419nm (λex=255 nm).Compound (7) has a one-dimensional ladder-like chain structure, and the asymmetric unit of (7) contains two Zn(Ⅱ) nucleus with four- and six-coordination model, respecsively. Two [ZnO4N2] octahedra are connected by one [ZnO4] tetrahedron to form trinuclear unit, the trinuclear units bridged by coner-shared oxygen atom to produce one-dimensional chain. The strong fluorescent emission bands of (7) is located at 359 nm (λex=263 nm).Compound (9) is a zero-dimensional structure, and the asymmetric unit of (9) contains two Cu(Ⅱ) nucleus with four-coordination model, respecsively. Fluorescent emission bands of (9) is located at 450 nm (λex=270 nm).Compound (10) is the first synthesized zero-dimensional organic adduct that containing the Pytpy. The maximum of the fluorescent emission bands of (10) is located at 427 nm (λex= 266 nm), with a shoulder at about 390 nm.The TG-DSC investigations show all compound’s structure are highly stable, and the collapse temperature of skeletons are (1)494℃, (2) 434℃, (3) 445℃, (4) 350℃, (5) 396℃, (6) 440℃, (7) 461℃, (8) 380℃, (9) 369℃, (10) 300℃, respectively. |
PDF Full Text Request