Synthesis, Characteration And Properties Of Coordination Polymers And Supramolecular Complexes Generated From Rigid Linear And Bent Organic Ligands

The chemistry of organic-inorganic coordination polymers has recently becomearea of increasing interest. Self-assembly of organic ligands and inorganic metal ionsis one of the most efficient and widely used approaches for the construction oforganic-inorganic composite materials. Recently, remarkable progress has been madein the area of molecular inorganic-organic hybrid compounds. The synthesis andcharaterization of infinite one-, two-, and three-dimensional networks have been anarea of rapid growth. In the thesis, a series of novel nano-sized bent 1, 3,4-Oxadiazole bridging ligands were synthesized. The coordination chemistry of thesenovel ligands with transition metal ions was investigated. In addition, two semi-rigid1, 3, 4-Oxadiazole-2-Thione bridging ligands and five rigid linear ligands have beendesigned and synthesized. The coordination chemistry based on them with metal ionswas investigated, too. Totally 27 new coordination polymers were prepared bysolution reactions and fully characterized by IR, elemental analysis and single-crystalX-ray diffraction. The solid state luminescent properties and host-guest chemistry ofselected polymeric compounds were investigated.1. The coordination chemistry based on nano-sized bent 1, 3, 4-Oxadiazolebridging ligandsThe coordination chemistry of the 1, 3, 4-Oxadiazole-bridging ligands withinorganic Ag(I) and Cu(II) salts has been investigated. Eleven new coordinationpolymers, namely [Ag₂(L1)(SO₃CF₃)₂]·(C₆H₆) (1), [Ag₂(L1)(SO₃CF₃)₂]·(C₆H₆)(2), [Ag(L1)]PF₆ (3), [Ag(L1)]SbF₆·(C₆H₆)·(THF) (4), [Ag(L1)]ClO₄·2.5(C₆H₆)(5), [Ag(L1)]BF₄·2.5(C₆H₆) (6), [Ag(L1)SbF₆]·unknown solvate (7),[Ag(L1)ClO₄]·(C₇H₈) (8), [Ag(L4)]ClO₄·1.5(C₆H₆)·THF (9),[Ag(L4)]BF4·1.5(C₆H₆)·THF (10), [Cu(L3)(C₅HF₆O₂)2] (11) were synthesizedbased on them, respectively. Their single crystal structures and luminescentproperties were investigated in the solid state.2. The coordination chemistry of the 1, 3, 4-Oxadiazole-2-Thione bridging ligandswith inorganic Ag(I), Cu(II), Zn(II) and Co(II) salts has been investigated. Ninenew coordination polymers, namely [Ag(L6)]SbF₆ (12), [Ag(L6)NO₃] (13),[Ag(L6)]BF₄ (14), [Ag(L6)]ClO₄ (15), [Ag(L6)SO₃CF₃] (16), [Ag(L7)SO₃CF₃](17), [Co(L6)₂(SCN)₂] (18), [Cu_0.5(L6)(C₅HF₆O₂)]·(CH₃OH) (19) ,[Zn(L6')2(H2O)4]·(H2O)2 (20)were synthesized based on them, respectively.Their single crystal structures and luminescent properties were investigated inthe solid state.3. The coordination chemistry of rigid linear ligands with inorganic Ag(I) andCu(II) salts has been investigated. Seven new coordination polymers, namely[Ag(L11)2]SO3CF3 (21), [Ag(L11)SbF6]·(C6H6) (22), [Ag(L12)2]SbF6 (23),[Ag(L12)(C6H6)2]SbF6·0.5(C6H6) (24), [Cu(L8)(C5HF6O2)] (25),[Cu3(L9)2(C5HF6O2)6] (26), [Cu(L10)(C5HO2F6)2] (27) were synthesized basedon them, respectively. Their single crystal structures were investigated in thesolid state.4. The role isomerism of L1, templating effect of polyatomic anions and solventintermediates on structures of Ag(I)-L1 coordination polymers were discussed.Host-guest chemistry of compound 6 were investigated. The experimental resultshows that 6 exhibits a clear affinity for benzene molecule, and can reversiblydesorb and re-absorb this guest molecule at room temperature.The results reported herein demonstrate that the use of nano-sized bent 1, 3,4-Oxadiazole bridging ligands, semi-rigid 1, 3, 4-Oxadiazole-2-Thione bridgingligands and rigid linear ligands as precursors to bind transition metal ions, is infact a new and efficient approach for synthesis of novel supramolecularnetworks with interesting physical properties.