合成具七員環氫鍵系統的激發態分子內質子轉移化合物

Abstract

在第一章裡，我們成功地利用Knoevenagel type 反應條件合成出具有雙功能性的鄰位綠色螢光蛋白質(o-HBDI)的衍生物，o-PyMeGFP，由於結構上的不穩定性，我們經過分子修正後成功地合成出o-PyPhGFP。o-PyPhGFP本身具有分子內七員環氫鍵經由激發態分子內質子轉移的過程放出607 nm的螢光。並且成功地將o-PyPhGFP與ZnCl2形成一錯合物(complex)，o-PyPhGFP-Zn，並且破壞其分子內氫鍵而放出466 nm的螢光。 在第二章裡，我們利用第一章的合成路徑，並且使用5-HI和7-HI作為起始物，成功地合成出具有locked form且剛固性較高的綠色螢光蛋白質中心發色團(p-HBDI)及其結構異構物(o-HBDI)的衍生物，分別為p-LHBDI和o-LHBDI。o-LHBDI經由ESIPT的過程放出585 nm的螢光，並且將量子產率提高到0.18。我們也成功地合成出對位(para-)及鄰位(ortho-)同時具有OH基的化合物，H2BDI。H2BDI以陰離子的形式放光在557 nm且量子產率為1.3 x 10-3。 在第三章裡，我們使用1,2-dibromocyclopent-1-ene 作為起始物，來連結pyridine與pyrrole兩個基團，成功地合成出新穎且具有分子內七員環氫鍵系統的化合物，7-HB。7-HB可經由ESIPT的過程放出603 nm的螢光。我們也成功地合成出將7-HB甲基化的化合物，7-NCH3。 在第四章裡，我們成功地合出三個可能具有分子內八員環氫鍵系統的化合物，分別為8-HB-1、8-HB-2、8-HB-3。

In part I, we successfully obtained the bifunctional ortho- green fluorescence protein (o-HBDI) derivative, o-PyMeGFP, synthesized by Knoevenagel type reaction. Due to unstable conformation of o-MePyGFP; However, we successfully synthesized o-PyPhGFP via molecular adjustment. o-PyPhGFP underwent excited-state intramolecular proton transfer process via seven-membered-ring hydrogen-bonding system and its emssion at 607 nm. Also, ZnCl2 was reacted with o-PyPhGFP to form a complex, which destructed intramolecular H-bond and obtained blue emission. In part II, according synthetic route from chapter1, 5-HI and 7-HI were used as starting reactants to obtain a structurally locked GFP core chromophore p-LHBDI, its ortho-derivative, o-LHBDI underwent ESIPT process and enhanced the quantum yield (up to 0.18) at 585 nm. We also synthesized H2BDI possessing both para- and ortho- hydroxyl groups. Anionic H2BDI rendered its emission at 557 nm and quantum yield of 1.3 x 10-3. In part III, 1,2-dibromocyclopent-1-ene was used as starting reactant to link pyridine and pyrrole to obtain the novel compound, 7-HB, possessing intramolecular seven-membered-ring H-bond system. 7-HB rendered tautomer emission at 603 nm. Also, we obtained the methylated compound, 7-NCH3. In part IV, three compounds (8-HB-1, 8-HB-2 and 8-HB-3) which were successfully synthesized may have intramolecular eight-membered-ring H-bond system.