透過您的圖書館登入
IP:44.200.77.59
  • 學位論文

含雙醯胺吡啶與多羧酸配位基之二價配位高分子的合成、結構與性質研究:金屬與配位基對結構的影響

Synthesis, Structures and Properties of Divalent Coordination Polymers Containing Bis-pyridyl-bis-amide and Polycarboxylate Ligands: Metal and Ligand Effect

指導教授 : 陳志德

摘要


藉由一系列不同長度與位向的雙醯胺吡啶與多羧酸輔助配位基搭配二價d7 - d10過渡金屬鹽類以水熱法合成出十種化合物: {[Ni(L1)(3,5-PDA)(H2O)3]·2H2O}n (L1 = N,N’-di(3-pyridyl)suberoamide, 3,5-H2PDA = 3,5-pyridinedicarboxylic acid), 1, {[Ni2(L1)2(1,3,5-HBTC)2(H2O)4]·H2O}n (1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid), 2, {[Ni(L2)(5-tert-IPA)(H2O)2]·2H2O}n (L2 = N,N’-di(3-pyridyl)adipoamide, 5-tert-H2IPA = 5-tert-butylisophthalic acid), 3, [Ni(L3)1.5(5-tert-IPA)]n (L3 = N,N’-di(4-pyridyl)adipoamide), 4, [Co(L1)(1,3,5-HBTC)(H2O)]n, 5, {[Co3(L1)3(1,3,5-BTC)2(H2O)2]·6H2O}n, 6, [Cu(L4)(AIPA)]n (L4 = N,N’-bis(3-pyridinyl)terephthalamide, H2AIPA = 5-acetamido isophthalic acid), 7, {[Cu(L2)0.5(AIPA)]·MeOH}n, 8, {[Zn(L4)(AIPA)]·2H2O}n, 9, {[Zn(L2)(AIPA)]·2H2O}n, 10。這些化合物藉由單晶X-ray繞射儀鑑定其結構,並以粉末X-ray繞射儀與熱重分析儀來研究化合物的特性。 化合物1具一維鏈狀結構,而化合物2具sql拓譜學之二維層狀結構。化合物3與4的差別在中性配位基的位向不同,前者為具63拓譜學的二維層狀結構,而後者為具(42·67·8)拓譜學的三維網狀結構。化合物5與6因反應時多羧酸配位基比例不同而有不同的結構,前者為具sql拓譜學的二維層狀結構,而後者為具(4·85)2(4)2(83)2(8)拓譜學之二維層狀結構,可進一步的簡化為63拓譜學構型。化合物7 - 10的合成差異在於運用不同柔軟度的中性配位基。化合物7具sql拓譜學之二維層狀結構,化合物8具pcu拓譜學之三維網狀結構,且具有2-fold的自我貫穿現象。化合物9與10皆為三維網狀結構,前者具8T2拓譜學,後者具(44·610·8)拓譜學。本文亦探討部分化合物的發光與光降解催化特性。

並列摘要


Ten divalent coordination polymers constructed from polycarboxylic acids and flexible bis-pyridyl-bis-amide ligands with different lengths and donor atom positions, {[Ni(L1)(3,5-PDA)(H2O)3]·2H2O}n (L1 = N,N’-di(3-pyridyl)suberoamide, 3,5-H2PDA = 3,5-pyridinedicarboxylic acid), 1, {[Ni2(L1)2(1,3,5-HBTC)2(H2O)4]·H2O}n (1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid), 2, {[Ni(L2)(5-tert-IPA)(H2O)2]·2H2O}n (L2 = N,N’-di(3-pyridyl)adipoamide, 5-tert-H2IPA = 5-tert-butylisophthalic acid), 3, [Ni(L3)1.5(5-tert-IPA)]n (L3 = N,N’-di(4-pyridyl)adipoamide), 4, [Co(L1)(1,3,5-HBTC)(H2O)]n, 5, {[Co3(L1)3(1,3,5-BTC)2(H2O)2]·6H2O}n, 6, [Cu(L4)(AIPA)]n (L4 = N,N’-bis(3-pyridinyl)terephthalamide, H2AIPA = 5-acetamido isophthalic acid), 7, {[Cu(L2)0.5(AIPA)]·MeOH}n, 8, {[Zn(L4)(AIPA)]·2H2O}n, 9, {[Zn(L2)(AIPA)]·2H2O}n, 10, were synthesized by hydrothermal reactions. These complexes were structurally characterized by using single-crystal X-ray diffraction and their properties investigated by using powder X-ray diffraction and thermal gravimetric analysis. Complex 1 forms a 1D chain, while complex 2 is a 2D layer with the sql topology. The bis-pyridyl-bis-amide ligands in 3 and 4 show different donor atom positions, resulting in a 2D layer with the 63 topology and a 3D network with the (42·67·8) topology, respectively. Different amounts of polycarboxylic acids in the preparations for complexes 5 and 6 were used, affording a 2D layer with the sql topology and a 2D network with the (4·85)2(4)2(83)2(8) topology, which can be further simplified to a 63 topology. Complexes 7 - 10 were prepared by the use of neutral ligands with different flexibility. While complex 7 is a 2D layer with the sql topology and complex 8 is a 2-fold interpenetrated 3D framework with the pcu topology, complexes 9 and 10 are 3D frameworks with the 8T2 and the (44·610·8) topologies, respectively. The emission properties and catalytic effect on the photodegradation of dye of some of the complexes are also discussed.

參考文獻


(23) H. -Y. He.; C. -H. Hsu.; H. -Y. Chang.; X. -K. Yang.; P. M. Chhetri.; D. M. Proserpio.; J. -D. Chen, Cryst. Growth Des., 2017, 17, 1991-1998.
(20) (a) T. -P. Tsai.; Y. -T. Huang.; U. Ray.; Y. -J. Chang.; P. -C. Cheng.; C. -J. Wu.; J. -D. Chen.; J. -C. Wang, Polyhedron, 2010, 29, 3081-3088; (b) W. -J. Huang.; C. -J. Hsu.; S. -K. Tsai.; H. -Y. He.; J.-J. Ding.; T. -W. Hsu.; C. -C. Yang.; J. -D. Chen, RSC Adv., 2015, 5, 23374-23382.
(7) X. -H. Bu.; W. Chen.; W. -F. Hou.; M. Du.; R. -H. Zhang.; F. Brisse, Inorg. Chem., 2002, 41, 3477-3482.
(14) Y. -H. Liao.; W. Hsu.; C. -C. Yang.; C. -Y. Wu.; J. -D. Chen. J.-C. Wang, CrystEngComm, 2013, 15, 3974-3983.
(10) (a) Y. -Q. Lan.; S. -L. Li.; J. -S. Qin.; D. -Y. Du.; X. -L. Wang.; Z. -M. Su.; Q. Fu, Inorg. Chem., 2008, 47, 10600-10610; (b) C. Qin.; X. -L. Wang.; E. -B. Wang.; Z. -M. Su, Inorg. Chem., 2008, 47, 5555-5557; (c) F. Luo.; Y. -T. Yang.; Y. -X. Che.; J. -M. Zheng, CrystEngComm, 2008, 10, 981-921.

延伸閱讀