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Title: | 對稱型 萘啶二胺配基異金屬串鉬 /鎳錯合 物之成與研究 Syntheses and Studies of the Hetero-polynuclear Mo/Ni Metal String Complexes Coordinated by Symmetric Naphthyridinyldiamine Tetradentate Ligand |
Authors: | Shih-Hong Li 李士弘 |
Advisor: | 彭旭明 |
Keyword: | 異金屬串錯合物、鉬鎳異金屬串錯合物、四核異金屬串錯合物、?啶二胺配基, Heterometallic metal string complex、hetero-polynuclear Mo/Ni complex、symmetric tetradentate ligand、naphthyridinyldiamin, |
Publication Year : | 2016 |
Degree: | 碩士 |
Abstract: | 本論文中以N2,N7-bis(4-methoxyphemyl)-1,8-naphthyridine-2,7-diamine
(H2DAniDANy)對稱型四氮配基,合成以鉬為主要金屬的系列異金屬錯合物,分別為[Mo2(HDAniDANy)4]BF4 (A)、Mo2Ni2(DAniDANy)4(B),並對這兩個金屬串錯合物進行其結構、磁性及電化學進行探討。 由X-Ray單晶繞射可得知,錯合物A是以四片HDAniDANy1-配基以螺旋式纏繞在兩個鉬金屬外圍,中間的鉬金屬以接近square planar的配位模式與氮原子鍵結。而錯合物B是以四片DAniDANy2-配基以螺旋式纏繞在四個金屬離子外圍形成金屬串,雙核鉬金屬以square planar的配位模式與氮原子配位於金屬串的一側,另一側的鎳金屬也以square planar的配位模式與氮原子配位,形成Mo-Mo-Ni-Ni的形式。 藉由晶體結構和磁性上的鑑定,藉由晶體結構與磁性行為上的鑑定,可得知錯和物A在300K時的μeff為1.68 B.M.,推測其電子自旋為Mo25+(S=1/2),接近純自旋理論的μeff = 1.73 B.M. , 推測錯合物A 的鉬鉬金屬為二三混價,其鍵長為2.1428(7)Å。 With the use of N2,N7-bis(4-methoxyphenyl)-1,8-naphthyridine- 2,7-diamine(H2DAniDANy), a symmetric tetradentate ligand, new series of HMSCs based on Molybdenum, [Mo2(HDAniDANy)4]BF4 (A)、Mo2Ni2(DAniDANy)4(B) were synthesized. The X-Ray structural studies showed that complex A are two Molybdenum wrapped by four HDAniDANy-1 ligands with 2,2-trans conformation, and metal ions with square planar geometry chelated by naphthyridine N atom and amido N atom of each HDAniDANy-1 . Complex B has two Molybdenum and two Nickel wrapped helically by four DAniDANy2- ligands, and the di-Molybdenum and di-Nickel with square planar geometry chelated by naphthyridine N atom and amido N atom of each DAniDANy2-, like Mo-Mo-Ni-Ni. The magnetic susceptibility showed that the μeff values of A at 300 K is 1.68 B.M. . The spin state of A with Mo25+(S=1/2) configuration, which is close to the spin-only value 1.73 B.M. . The complex A is an mixed-valence di-Molybdenum with Mo(II)/Mo(III), which bond length is 2.1428(7) Å. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/50838 |
DOI: | 10.6342/NTU201600814 |
Fulltext Rights: | 有償授權 |
Appears in Collections: | 化學系 |
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ntu-105-1.pdf Restricted Access | 4.35 MB | Adobe PDF |
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