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Title: 含硒之過渡金屬 (鐵、銅) 聚合物的合成及物性與光降解有機物的反應性之探討
Ternary Se−Fe−Cu Carbonyl Coordination Polymers: Mechanochemical Synthesis, Reversible Structural Transformations, Semiconducting Properties, and Photodegradation
Authors: 謝明惠
Shieh, Minghuey
Huang, Kai-Ting

Issue Date: 2020
Abstract: 利用 [Et4N]2[SeFe3(CO)9] 及 [Cu(MeCN)4][BF4] 以當量比 1: 2 ,並分別與劑量的含氮配體 4,4’-dipyridine (dpy)、1,2-bis(4-dipyridyl)ethane (bpea) 或 4,4’-trimethylenedipyridine (bpp) 進行三組件 (three-components) 溶劑輔助研磨 (liquid-assisted grinding, LAG) 反應,可分別形成含硒之混合鐵銅羰基一維聚合物 [SeFe3(CO)9Cu2(L)3]n (L = 4,4’-dipyridine (dpy), 2)和[SeFe3(CO)9Cu2(L)]n (L = 1,2-bis(4-dipyridyl)ethane (bpea), 3; L = 1,2-bis(4-dipyridyl)ethene (bpee), 5)、二維聚合物 [SeFe3(CO)9Cu2(MeCN)(dpy)1.5]n (1), [SeFe3(CO)9Cu2(L)2.5]n (L = bpea, 4; L = bpee, 6) 和 [SeFe3(CO)9Cu2(L)2]n (L = 4,4’-trimethylenedipyridine (bpp), 8) 以及大環分子型化合物 [{SeFe3(CO)9Cu2}2(bpp)2] (7)。此系列聚合物亦可藉由溶劑輔助研磨方式 (LAG) 進行可逆的結構轉換。由固態反射式紫外/可見光光譜可得知聚合物 1─6 和 8 及化合物 7 皆具有半導體的特性。 基於聚合物 1─6 和 8 的半導體性質,欲利用其電子傳導特性進行光降解有機物。因此,本研究利用較穩定的聚合物2、4 和 8 對4-硝基苯酚 (PNP) 和甲基藍 (MB) 進行光照降解,實驗結果顯示聚合物 2、4 和 8 於水溶液中照射紫外至可見光波長的氙燈的條件下,可成功並快速的降解 4-硝基苯酚 (PNP) 和甲基藍 (MB),顯示此系列聚合物具有優異的光降解活性。此外,本系列 Se‒Fe‒Cu 聚合物之Cu 金屬的氧化態,亦藉由高解析率 X-ray 光電子能譜 (X-ray photoelectron spectroscopy, XPS) 和 Cu K-edge X-ray 吸收近邊結構光譜 (X-ray absorption near-edge spectroscopy, XANES) 進一步驗證,其結果顯示於聚合物 1─6 和 8 中的 Cu 原子氧化態介於 CuI 和 Cu0 之間並接近 Cu0 的中間氧化態,顯示聚合物中含硒之三鐵金屬團簇可提供並傳遞電子至 CuI 中心並經由含氮配體使其電子可有效的傳遞。
A series of semiconducting cluster-incorporated Se−Fe−Cu coordination polymers, 1D polymers [SeFe3(CO)9Cu2(L)3]n (L = 4,4’-dipyridine (dpy), 2) and [SeFe3(CO)9Cu2(L)]n (L = 1,2-bis(4-dipyridyl)ethane (bpea), 3; L = 1,2-bis(4-dipyridyl)ethene (bpee), 5), 2D polymers [SeFe3(CO)9Cu2(MeCN)(dpy)1.5]n (1), [SeFe3(CO)9Cu2(L)2.5]n (L = bpea, 4; L = bpee, 6), and [SeFe3(CO)9Cu2(L)2]n (L = 4,4’-trimethylenedipyridine (bpp), 8) as well as the macrocycle [{SeFe3(CO)9Cu2}2(bpp)2] (7) have been synthesized via the liquid-assisted grinding (LAG) from the three-component reaction of [Et4N]2[SeFe3(CO)9], [Cu(MeCN)4][BF4], and conjugation or conjugation-interrupted dipyridyl linkers in high yields, respectively. Their reversible structural transformations were also successfully achieved via the mechanochemical synthesis by adding the corresponding agents, [Et4N]2[SeFe3(CO)9], [Cu(MeCN)4][BF4], and dipyridyl linkers with stoichiometric amounts. Notably, their energy gaps were found to reach the semiconducting region. Based on their semiconducting behaviors, it was surprising to find that our synthesized Se−Fe−Cu polymers 2, 4, and 8 exhibited excellent activity toward the photodegradation of p-nitrophenol (PNP) and methylene blue (MB) by the low-wavelength xenon lamp in aqueous solutions. In addition, high-resolution X-ray photoelectron spectroscopy (XPS) and Cu K-edge X-ray absorption near-edge spectroscopy (XANES) showed that all of the Cu atoms in polymers 1–6 and 8 were in an intermediate oxidation state between CuI and Cu0 and close to Cu0. The results clearly indicated that [SeFe3(CO)9]2− acted as an electron-donating moiety to transport electrons into the CuI centers in our synthesized polymers, which could facilitate efficient electron transport within these 1D or 2D coordination polymers, resulting in their semiconducting behavior.
Other Identifiers: G060642046S
Appears in Collections:學位論文

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