含十六族(硒、碲)之過渡金屬(鐵、銅)聚合物的合成與小分子選擇性及物性之探討

Abstract

Se,Te ‒Fe‒Cu‒p-DCB 系統 過去實驗室得一維單－雙股橋接 (singly-doubly linked) Z 字線型 (zigzag chain) 聚合物 [EFe3(CO)9Cu2(p-DCB)1.5]n (E = Te, 1a; Se, 1b)。另一方面，由固態反射式紫外光/可見光光譜可得知一系列含有客分子之聚合物 1a-S (S = toluene, m-xylene, p-xylene, ethylbenzene, pseudocumene, mesitylene, naphthalene) 之能隙範圍在 1.27‒1.41 eV，皆小於主體結構聚合物 1a (1.43 eV)，顯示皆具半導體特性。

Se‒Fe‒Cu 系統 利用零維分子型環狀化合物 [{SeFe3(CO)9Cu}2(bpp)2] (1) 加入含氮配子 4,4’-trimethylenedipyridine (bpp) 研磨後，可得二維聚合物 [SeFe3(CO)9Cu2(bpp)2] (2)。此系列聚合物之能隙範圍為 1.51-1.65 eV，皆具有半導體之特性，其熱穩定區間為 90 至 175 oC 之間。此外，當化合物 [SeFe3(CO)9Cu2(MeCN)2] 與混合硫/氮之有機配子 4,4'-dipyridyl sulfide (tdpy) 研磨得到一維聚合物 [SeFe3(CO)9Cu2(MeCN)(tdpy)2]n (7)。

Se,Te‒Fe‒Cu‒p-DCB system Two new one-dimensional singly-doubly linked zigzag chain polymers [EFe3(CO)9Cu2(p-DCB)1.5]n (E = Te, 1a; Se, 1b) were synthesized. In addition, the solid-state diffused reflectance spectra revealed that the energy gap of polymers 1a-S (S = toluene, m-xylene, p-xylene, ethylbenzene, pseudocumene, mesitylene, naphthalene) ranged from 1.27 to 1.41 eV, lower than that of polymer 1a (1.43 eV), which was mainly attributed to the C-H… interaction within the framework of the polymeric derivatives.

Se‒Fe‒Cu system When [{SeFe3(CO)9Cu2}2(bpp)2] (1) was treated with bpp via the liquid-assisted grinding (LAG) method, a 2D macrocyclic polymer [SeFe3(CO)9Cu2(bpp)2]n was obtained. Moreover, one-dimensional polymer [SeFe3(CO)9Cu2(MeCN)(tdpy)2]n (7), structurally anaologous to the dipyridyl-linked polymer [SeFe3(CO)9Cu2(dpy)3]n (4), was obtained from [SeFe3(CO)9Cu2(MeCN)2] with tdpy. Importantly, solid-state diffuse reflectance spectra showed these Se−Fe−Cu polymers exhibited semiconducting behaviors with the low energy gaps of 1.51 eV to 1.63 eV.