我們設計了一個三元件系統，其中包含了鍵結中心(pyrrole)、反應中心(porphyrin)及連結前面兩者的共軛架橋，當反應中心的紫質被金屬化時，會誘使系統進行分子內的電荷轉移，而改變了遠端鍵結中心的氫鍵鍵結能力。本篇研究是以理論計算的方式，對紫質三元件系統進行兩項探討，第一項研究是關於金屬化作用對於不同取代位置的紫質三元件系統的影響，藉此來了解紫質三元件系統在遠端氫鍵鍵能的調控上是否有位置選擇性。在這一方面我們發現一般的紫質系統並不適合作為反應中心，金屬化前後並未帶來明顯的氫鍵鍵能變化，所以改以不同雜環取代的heteroporphyrin來做研究，而得到了很好的氫鍵調控能力；第二項研究則是利用相同或不同的架橋，使得金屬化對於各個方向的氫鍵作用力達到相同或有差異性的調控，並且研究當系統延伸至多個方向時，被多個鍵結中心瓜分的中心金屬電荷，對遠端的氫鍵鍵能是否還有調控的能力。 Remote control of hydrogen bond strengths can be modulated in a three-component system containing a hydrogen bonding site(pyrrole),a conjugated bridge and a reaction center (porphyrin). Metalation of the reaction center can trigger intramolecular charge transfer(ICT), thus altering the binding ability of the remote hydrogen-bonding site. In our computational study, we have investigated two topics. The first one is to study the effect of metalation in the porphyrin three-component systems with different bridge positions. In this case, we have found that the porphyrin ring does not induce ICT in the metalated states, so we changed the reaction center to heteroporphyrins. Remote control of hydrogen bond strengths was successfully achieved with heteroporphyrins. The second topic is to construct two different types of multiple-way control systems which have multiple binding sites controlled by one metalation center. One has the similar binding strengths at all binding sites and the other has different binding strengths. We also compare the effectiveness of metalation in terms of remote control in single-way and multiple-way systems.
