本論文主要為合成三氮配基Hphany,全名為2-Phenylamino-1,8-naphthyridine,並用此配基與鎳(II)金屬、釕(II)金屬,以實驗室所開發的萘燒技術合成直線形的金屬串錯合物。並且在苯環上相對於氮對位的地方修飾-CF3、-OMe,以期在鍵長、UV、CV能夠做比較。另外本論文也合成了六氮配基H2napany,全名為2-(naphthyridylamino)-7-phenylamino-1,8-naphthyridine,並嘗試合成六核鎳金屬串錯合物。 成功地合成出三氮配基、修飾的三氮配基、六氮配基,並且也順利合成出其金屬串錯合物。而由於配基屬於不對稱形配基,因此金屬串錯合物有所謂的異構物,以苯環的位置可區分(4,0)、(3,1)、(2,2-cis)、 (2,2-trans)…等四種構形,而合成出的三核鎳金屬串錯合物,經過X-ray單晶解析,由於軸向配基NCS的立體阻礙不大,造成彼此間屬於不同種構形,因此鍵長、CV、UV較難去做比較。若以氯為軸向配基所合成出的金屬串錯合物,可以藉由氯與苯環的steric effect去控制形成(4,0) form,例如三核釕金屬串錯合物與六核鎳金屬串錯合物。其中六核鎳金屬串錯合物發現在萘啶單元有還原一個電子的性質,此現象與二萘啶胺系統一樣,所以鍵長可以做詳細的比較。 磁性量測方面,鎳金屬串兩端有軸向配基,是屬於反鐵磁性,若是只有一端有軸向配基,則呈現順磁性。結果頗符合我們所預測的。
This thesis is presented to study the crystal structures and physical properties of the linear polymetal complexes. The major geometries of these complexes are composed of the linear polymetal core surrounded by the ligands:Hphany、Hmophany、Htfmphany and H2napany. Since these ligands are unsymmetrial, these complexes may have several different isomeric forms. These forms could be assigned as (4,0)、(3,1)、(2,2-trans) and (2,2-cis) according to the orientation of the phenyl groups. In the research of the linear polymetal complexes, the isomeric forms may result from the size of the different axial ligands. If the axial ligand is NCS-, several kinds of isomers including (2,2-trans)、(2,2-cis) and (3,1) forms could be obtained due to the weak steric effect. However, the (4,0) form will be the major product when the axial ligand is Cl- which causes strong steric hindrance. Furthermore, the linear hexanickel complex have been reduced during synthesis without adding reducing agents. This phenomenon is similar to the [Ni5(bpy)Cl2](PF6)2 (bpy = binaphthyridiylamine). The SQUID experiments of these linear trinickel complexes which have two axial ligands show strong antiferromagnetic coupling which are similar to the Ni3(dpa)4Cl2. On the other hand, the linear polymetal complexes which are (3,1) and (4,0) forms only have one magnetic center which could be observed in the SQUID experiments.