含二硒磷酸配位基之鋅金屬簇錯化合物之研究及利用Cu4[Se2P(OC3H7)2]4經由SSCVD合成Cu2-xSe 奈米導線

Research of Zinc Clusters Containing Dialkyl Diselenophosphate Ligands, Synthesis of Cu2-xSe Nanowires from the Cluster Cu4[Se2P(OC3H7)2]4 via SSCVD Process

洪秋明(Hung Chiu-Mine)

指導教授 ： 楊千金

中原大學/理學院/化學研究所/博士(2005年)

https://doi.org/10.6840/cycu200500174

摘要

利用Zn(ClO4)2˙6H2O與NH4[Se2P(OR)2] (R = Et、Pr、iPr)室溫下莫耳比例1：2在H2O中反應，我們可以分離出一系列具有中心原子的二種扭曲四面體[Zn4(m4-Se){Se2P(OR)2}6]與[Zn4(m4-O){Se2P(OR)2}6] (R = Et, Pr, iPr)。此類的金屬簇錯化合物包含了六個位於邊上的橋接二硒磷酸配位基(O,O’-dialkyl diselenophosphato, dsep)與四個位於四面體的金屬原子包含著一個位於中心的硒或氧原子。所有的金屬原子是被橋接的dsep配位基所連結，而形成一個雙金屬雙配位的型式(2, η2)。每一個金屬原子是銜接由三個橋接配位基所提供的三個硒原子及一個中心硫族原子，此外由十二個2-橋接的硒原子形成二十面體型，當此架構中包含有硫族中心時可以發現總計由四個四面體型及四個含有金屬中心的四面體型所組合而成。由變溫的31P NMR中可以觀察到[Zn4(m4-Se){Se2P(OR)2}6]是非常容易解離成[Zn{Se2P(OR)2}2]的結構，而此單核結構在溶液中又易於與雙核金屬簇錯化合物[Zn{Se2P(OR)2}2]2形成平衡狀態。
我們成功的利用了金屬簇錯化合物Cu4[Se2P(OC3H7)2]4為前趨物經由SSCVD的方法以self-catalytic vapor-liquid-solid的生長機構去形成1D的奈米結構，此金屬簇錯化合物 Cu4[Se2P(OC3H7)2]4被用來製成Cu2-xSe奈米導線及去描述可能存在的應用性。

關鍵字

一維奈米結構 ； 鋅 ； 金屬簇錯化合物 ； 奈米導線 ； 二硒磷酸配位基

並列摘要

Two types of discrete tetrahedron with a chalcogenide atom in the center, [Zn4(m4-Se){Se2P(OR)2}6] and [Zn4(m4-O){Se2P(OR)2}6] (R = Et, Pr, iPr), were formed from the reaction of Zn(ClO4)2˙6H2O and NH4[Se2P(OR)2] (R = Et, Pr, iPr) in a molar ratio of 1 : 2 in H2O at room temperature. The cluster consists of six edge-bridged O, O’-dialkyl diselenophosphato (dsep) ligands and four metal atoms in a tetrahedron with selenium or oxygen atom in the center. All of the metal atoms are connected by bridging dsep ligands. Thus the dsep ligands exhibit a bimetallic biconnective (2, η2) coordination pattern. Each metal atom is coordinated by three selenium atoms from three bridging dsep ligands and one central chalcogen atom. In addition, twelve 2-bridging selenium atoms form a Se12 icosahedron. Thus the framework, a chalcogenide-centered icosahedron, consists of a total of eight tetrahedral holes of which one-half is occupied by the zinc ions. From variable temperature 31P NMR studies it has been observed that the cluster, [Zn4(m4-Se){Se2P(OR)2}6], is partly decomposed to [Zn{Se2P(OR)2}2] and the monomeric species is further in equilibrium with its dimer [Zn{Se2P(OR)2}2]2.
We were successful to utilize metal cluster of Cu4[Se2P(OC3H7)2]4 as precursor of SSCVD reactor with the self-catalytic vapor-liquid-solid growth mechanism for 1D nanostructure. The cluster Cu4[Se2P(OC3H7)2]4 was used as the precursor for preparation of Cu2-xSe nanowires in a hot-wall CVD reactor as an illustration of potential applications of the cluster.

並列關鍵字

cluster ； 1 D nanostructure ； dialkyl diselenophosphato ； Zinc ； nanowires

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