- 學位論文
Design, Synthesis, Luminescence and Catalysis of Coordination Frameworks Containing Ag(I), Cu(II), Zn(II) and Cd(II)
Design, Synthesis, Luminescence and Catalysis of Coordination Frameworks Containing Ag(I), Cu(II), Zn(II) and Cd(II)
並列摘要
Interesting structural, spectroscopic, luminescence and catalytic properties of coordination polymers are presented and discussed in this dissertation. In chapter 3, we have shown that 1-D zigzag chains of {[Ag(BPYB)](ClO4)•0.5Et2O}n (3.1), {[Ag(BPYB)](OTf)•Et2O}n (3.2), and {[Ag(BPYB)](BF4)•0.5CH3OH}n (3.3) were obtained from the reaction of AgClO4, AgCF3SO3, and AgBF4 with 1,4-bis(pyridine-3-ylethynyl)benzene (BPYB) in similar reaction conditions respectively, whereas it led to the formation of a 1-D sinusoidal chain of {[Ag(BPYB) (NO3)]•H2O}n (3.4) and a metallolocycle of [Ag2L6](BF4)2 (4.5) in a different reaction procedure for the AgNO3 and AgBF4 cases. Complexes 3.1 – 3.3 form 1-D zigzag chains and every two chains are further stacked to give a pair of chains assisted by weak Ag(I)•••Ag(I) and π•••π interactions, whereas a single 1-D sinusoidal chain of 3.4 can be only obtained. It is noted that only the bridging L ligands in 5 adopt a syn conformation, whereas those in 3.1 – 3.4 are in an anti conformation. In this regard, this work has demonstrated the delicate effects of anions and reaction conditions on the assembly reactions of complexes 3.1 – 3.5. In addition, a structural transformation process had been observed during the heating process for 3.5. Although the powder X-ray diffraction pattern of 3.5 at 210 oC is similar to that of 3.3, it cannot be conclusively proven by powder X-ray diffraction studies due to the presence of some mismatches between both patterns of 3.5 and 3.3. In chapter 4, we have shown that six coordination polymers based on C3-symmetric flexible ligand N,N′,N′′-tris(4-pyridinylmethyl)-1,3,5-benzene-tri-carboxamide (TPBTC), namely, {[Cd(NO3)2(TPBTC)]∙(DMA)}n (4.1), {[Cd(IPA)(TPBTC)]∙(DMF)1.5(H2O)2}n (4.2), {[Cd(MeO-IPA)(TPBTC)]∙(DMF)3(EtOH)(H2O)3}n (4.3), {[Cd(NO2-IPA)(TPBTC)]2}n (4.4), {[Cd(TDC)(TPBTC)]3}n (4.5), {[Cd3(BDC)3(TPBTC)2(H2O)3]2∙(DMF)2∙(H2O)17}n (4.6) (where H2IPA = Isophthalic acid, H2MeO-IPA = 5-methoxy isophthlic acid, H2NO2-IPA = 5-nitro isophthalic acid, H2TDC = 2,5-thiphenedicarboxylic acid, H2BDC = 1,4-benzenedicarboxylic acid), were synthesized and characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, themogravimetric analysis, FT-IR, and NMR spectroscopy. In attempt to synthesized a mix-ligand crystal, Cd(NO3)2∙4H2O and TPBTC in presence of 2,6-naphthalenedicarboxylic acid under solvothermal condition furnished a new 2D→3D polycatenated homo-ligand architecture which simultaneously possesses Cd3TPBTC2 cage Cd6TPBTC6 ring. Iso-structural 2-D bilayer networks were obtained when TPBTC were treated with different isophthalic acid derivatives under almost similar condition. Only complex 4.6 crystallized as highly entangled 3-D polymeric network. In chapter 5, we have shown the synthesis of a pair of new C2-symmetric semi-rigid carboxamide ligands with one carboxylate and two pyridyl groups, namely 3,5-bis(isonicotinamido)benzoic acid (HBINAB) and 3,5-bis(nicotinamido)benzoic acid (HBNAB). With HBINAB a series of compounds were developed with various metal salts ZnX2 (ClO4-, BF4-, Cl-), CdX2 (NO3-, Cl-), CuX2 (ClO4-). Different zinc salts gave rise to different 2-D networks: perchlorate salt provided 2-fold interpenetrated {[Zn(BINAB)2]∙3H2O}n (5.1), tetrafloroborate salt provided non-interpenetrated {[Zn(BINAB)(DMF)(MeOH)](BF4)∙(DMF)}n (5.2), chloride salt provided 2-fold interpenetrated {[Zn(BINAB)Cl]2∙(DMF)(H2O)5}n (5.3). Cd-salts produce iso-structural {[Cd(NO3)(BINAB)]2∙(DMF)}n (5.4), {[CdCl(BINAB)]2}n (5.5). The Cu-complex {[Cu2(μ2-Cl)(BINAB)2]}n (5.6) only led to uniqe 3-D porous network with solvent accesible void 61.1 % (excluding perchlorate anion), this work has demonstrated anions and reaction conditions directed assembly reactions of complexes 5.1 – 5.5. The only homoligand complex of HBNAB, {[Cd(BNAB)2]∙5H2O}n (5.7), also crystalized a 2-D network. We also synthesized a series of mix-ligand coordination polymers, namely, {[Cd3(HCO2)2(BPDC)(BINAB)2(H2O)]∙(DMF)2(H2O)2}n (5.8), {[Cd2(BTC)(BINAB)(DMF)(H2O)3]∙(H2O)4}n (5.9), {[Cd2(IPA)2(BINAB)]∙(Me2NH2)(DMF)(H2O)}n (5.10), {[Cd6(NDC)6(BINAB)3]}n (5.11), {[Cd2(BDC)(BNAB)2(DMF)2]∙(DMF)3(H2O)4}n (5.12).