中文摘要
本篇論文之旨趣在於學習生化系統中蛋白質結構的設計建構原理，應用氫鍵作用引導每個獨立的金屬-有機建構單元，以自組裝方式製備各式的特殊結構。首先設計金屬-水合酸錯合物 [M(pdc)(H2O)5] · 2H2O (H2pdc = 3,5-啶二酸) (M = Co, Ni) ，該模組單元具有可形成氫鍵作用之donor-acceptor配對，再利用水熱條件調控自組裝成5種新配位網狀聚合物 [Co2(bpy)(pdc)2(H2O)4 · 4H2O]n ( 1 )、[Ni2(bpy)(pdc)2(H2O)4 · 4H2O]n ( 2 )、[Co2(bpym)(pdc)2(H2O)4 · 2H2O]n ( 3 )、 [Ni2(bpym)(pdc)2(H2O)4 · 2H2O]n ( 4 ) 、 [Ni(pdc)(H2O)]n ( 5 ) (bpy = 2,2'-聯啶，bpym = 2,2'-聯嘧啶)。本文將探討這些化合物結構上的特性並對其應用性進行分析與討論。
金屬-水合酸錯合物 [Ni(pdc)(H2O)5] · 2H2O 以及化合物 1 、 2 、 3 、 4 、 5 已由X射線單晶繞射獲得晶體結構其相關數據如下所示:
[Ni(pdc)(H2O)5] · 2H2O 之天藍色晶體屬立方晶系，空間群 Cmc21，a = 11.682(2) Å，b = 15.737(2) Å，c = 7.023(6) Å，最後Rf = 0.035。為一單分子錯合物。
( 1 ) 之橘紅色晶體屬三斜晶系，空間群P ，a = 9.539(2) Å，
b = 12.352(3) Å，c = 16.641(7) Å，α = 84.71(3)°，β = 73.74(3)°，γ= 86.77(2)°，最後Rf = 0.054。其結構為由氫鍵連結成之三維網狀聚合物。
( 2 ) 之淺藍色晶體屬三斜晶系，空間群P ， a = 9.508(2) Å，
b = 12.286(2) Å，c = 16.656(3) Å，α = 84.57(0)°，β = 73.88(0)°，γ= 86.49(0)°，最後Rf = 0.057。其結構為由氫鍵連結成之三維網狀聚合物。
( 3 ) 之橘紅色晶體屬三斜晶系，空間群P ， a = 6.985(1) Å，
b = 8.334(2) Å，c = 11.944(2) Å，α = 109.54(1)°，β = 94.042(1)°，γ= 101.86(0)°，最後Rf = 0.045。分子為由氫鍵支持之三維聚合物，有一個反置中心位於bpym 配子上C4-C4A 軸中間。
( 4 ) 之深綠色晶體屬三斜晶系，空間群P ， a = 7.028(1) Å， b = 8.390(3) Å，c = 11.818(4) Å，α = 110.16(2)°，β = 93.46(1)°，γ= 103.12(1)°，最後Rf = 0.036。分子為由氫鍵支持之三維聚合物，有一個反置中心位於bpym 配子上C4-C4A 軸中間。
( 5 ) 之深綠色的晶體屬單斜晶系，空間群P21/c，a = 7.749(1)
Å，b = 15.040(3) Å，c = 6.427(1) Å，最後Rf = 0.042。其結構為長短磚型的三維網狀結構。

Abstract
The employment of the mechanism in protein systems into transition metal-organic coordination network provides a more flexible strategy for organizing individual molecular motifs or building blocks into diverse network topologies. We have been interested in the rational design and synthesis of metal-organic coordination network containing novel network topology and functionality via the modular building unit approach. Expanding on this approach in the search of appropriate modular units for the assembly of functional polymeric networks, we conceive a new strategy for the design of hydrogen bonding donor-acceptor unit on the basis of an aqua-metal carboxylate complex, [M(pdc)(H2O)5] · 2H2O (H2pdc = 3,5-pyridinedicarboxylic acid) (M = Co, Ni). The modular complex, M(pdc)(H2O)5, serves as a [aqua-metal]HO–H···O[carboxylate] H-bonding donor-acceptor pair and are responsible for the formation of the 3-D supramolecular framework.
We treated the aqua-metal carboxylate complex [M(pdc)(H2O)5] · 2H2O with bpy or bpym (bpy = 2,2'-bipyridine, bpym = 2,2'-bipyrimidine) by the hydrothermal method to give five new complexes. Crystal structures of the complexes [M(pdc)(H2O)5] · 2H2O and 1, 2, 3, 4, 5 have been determined by the X-ray diffraction method.
[M(pdc)(H2O)5] · 2H2O, orthorhombic, space group Cmc21, a = 11.682(2) Å, b = 15.737(2) Å, c = 7.023(6) Å. Final Rf = 0.035.
( 1 ), triclinic, space group P , a = 9.539(2) Å, b = 12.352(3) Å, c = 16.641(7) Å, α = 84.71(3)°, β = 73.74(3)°, γ= 86.77(2)°. Final Rf = 0.054 .
( 2 ), triclinic, space group P , a = 9.508(2) Å, b = 12.286(2) Å, c = 16.656(3) Å, α = 84.57(0)°, β = 73.88(0)°, γ= 86.49(0)°. Final Rf = 0.057.
( 3 ), triclinic, space group P , a = 6.985(1) Å, b = 8.334(2) Å, c = 11.944(2) Å, α = 109.54(1)°, β = 94.042(1)°, γ= 101.86(0)°. Final Rf = 0.045.
( 4 ), triclinic, space group P , a = 7.028(1) Å, b = 8.390(3) Å, c = 11.818(4) Å, α = 110.16(2)°, β = 93.46(1)°, γ= 103.12(1)°. Final Rf = 0.036.
( 5 ), monoclinic, space group P21/c, a = 7.749(1) Å, b = 15.040(3) Å, c = 6.427(1) Å. Final Rf = 0.042.

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