| In the past decades, inorganic-organic hybrid coordination polymers have attractedmuch attention not only because of their intriguing structural topologies but also theirpotential applications in catalysis, gas storage or separation, luminescence, magnetism,and conductivity. The N-or S-containing heterocyclic ligands have been extensivelyemployed in the assembly of the [CunIn]-based coordination polymers. The mixed N,S-donor ligands have also been attracted some attention because these ligands cancoordinate Cu(I) atoms with different coordination atoms. However, bi-orpoly(pyrimidylthio) ligands have less been used to construct [CunIn]-based coordinationpolymers. In this thesis, we prepared a set of relatively bulk4-phenylpyrimidine-2-thio-based ligands with different alkyl (CH2)n spacers. Reactionsof CuX with these ligands afforded a family of nine1D and2D [CunIn]-basedcoordination polymers. These compounds were characterized by elemental analysis, IR,single-crystal X-ray crystallography. Their photoluminescent properties were alsoinvestigated.In MeCN and CHCl3, reactions of CuI with [(phpy)(CH2)n(phpy)](phpyH=4-phenylpyrimidine-2-thiol; n=1, bphpym; n=2, bphpye; n=3, bphpypr; n=4,bphpyb; n=5, bphpyp; n=6, bphpyh) ligands afforded six new1D and2D[CunXn]-based coordination polymers [{Cu(μ3-I)}2(phpym)]n(1),[{Cu(μ3-I)}4(bphpye)]n(2),[{(MeCN)Cu3(μ-I)2(μ4-I)}2(bphpypr)2]n(3),[{((MeCN)Cu)(μ-I)}2(bphpyb)]n(4),[{Cu2(μ-I)(μ3-I)}2(bphpyp)2]n(5) and[{((MeCN)Cu)(μ3-I)}2{Cu(μ-I)}2(bphpyh)2]n(6). The3D framework of bulk CuI wascracked by the ligands into staircase [Cu2I2]nchain (1and2), double butterfly-shapedhexanuclear [Cu3(μ-I)2(μ4-I)]2units (3), dinuclear [Cu(μ-I)]2units (4), chairliketetranuclear [Cu4(μ-I)2(μ3-I)2] units (5) and rhomboid tandem [Cu2I2]nchain (6). These resulting units are further interconnected via ditopic flexible ligands to form new1Dchain or2D networks. The photoluminescent properties of them were also studied. It isnoted that the maxima emission of1-6are red-shifted compared to those of thecorresponding ligands.The similar reactions of CuBr with bphpye, bphpyb, or bphpyp resulted in theformation of [Cu2(μ-Br)2bphpye]n(7),[{(MeCN)Cu3(μ-Br)2(μ4-Br)}2(bphpypr)2]n(8)and [{(MeCN)Cu2(μ-Br)(μ3-Br)}bphpyp)]n(9), respectively. Complexes7-9wereconfirmed by elemental analysis, IR, and X-ray crystallography. The [CunBrn] structuralmotifs are collected by bphpye, bphpyb, or bphpyp, forming new1D chain or2Dnetworks. |
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