Synthesis, Structure, and Photophysical Properties of Zinc(II)-Salicylidenimine Complexes and Their Reactivities toward Transition Metal Ions

[[abstract]]在本論文第一個部分為合成三個具有Schiff base 的有機配子HS3py，HClS3py，HOMeS3py，將這三個有機配子分別與Zn，Cu，Co，Ni等過渡金屬鹽反應，可以得到一系列的過渡金屬錯合物[ML2] (M=Zn, Cu, Co, Ni; L = S3PY, ClS3PY, 和OMeS3PY)，經NMR、質譜、元素分析鑑定，並利用X光單晶繞射儀探討其固態結構，以及利用紫外光可見光光譜儀與螢光光譜儀探討其光物理性質。其中鋅金屬錯合物之鋅金屬離子和其他的過渡金屬離子Cu2+，Co2+，Ni2+，Pd2+與Ag+，在本研究中以紫外光可見光光譜以及螢光光譜偵測反應的情形。實驗結果顯示過渡金屬Cu, Co, Ni 與Pd會成相對應之ML2錯合物，取代鋅金屬離子的能力依序為Cu>Ni>Co>Zn。此一取代反應似乎與配子上取代基推拉電子能力有關(電子效應)；拉電子基團有助於此一取代反應，而推電子基團則會抑制此一取代反應的發生。在與銀金屬鹽的反應中，銀梨子並不會取代鋅金屬中心，而是會與鋅金屬錯合物上?啶基之氮原子配位，且配位後會使螢光強度增強。 本論文第二個部分以上述合成之過渡金屬錯合物Cu(S3py)2、Ni(ClS3py)2分別與2,6-?二酸、鋅鹽、?啶與二甲基乙醯胺行溶劑熱合成，得到兩個二維具通道的配位聚合物[Cu2(NDC)2(py)2]n與[Ni2(NDC)2(py)2]n，探討其結構與物性，並以熱重分析，粉末X光繞射，元素分析來觀測這兩個配位聚合物與其他溶劑的吸附現象。實驗結果顯示[Cu2(NDC)2(py)2]n與[Ni2(NDC)2(py)2]n經高溫處理去除?啶分子後，均可吸附?啶、乙?與水分子，另外[Ni2(NDC)2(py)2]n表現較佳的堆疊回復能力與熱穩定性。[[abstract]]Three Schiff bases, HS3PY, HClS3PY, and HOMeS3PY, have been designed and synthesized from the condensation reaction of 3-aminopyridine and corresponding salicylaldehydes. Reactions of the prepared Schiff-base ligands and zinc, copper, cobalt, nickel salt afforded corresponding metal–salicylideneimine complexes with a general formula [ML2] (M = Zn, Cu, Co, Ni; L = S3PY, ClS3PY, and OMeS3PY). Their molecular structures are characterized by 1H-NMR, MS, and element analysis The zinc–salicylideneimine complexes exhibit photoluminescence properties (505 nm for Zn(S3py)2, 512 nm for Zn(ClS3py)2, and 565 nm for Zn(OMeS3py)2) in methanol at room temperature, which are stronger in intensity than these showed by the organic ligands. When zinc–salicylideneimine complexes are reacted with transition metal salts (Cu(OAc)2, Co(BF4)2, Ni(BF4)2, PdCl2), a cation-ion exchange reaction occurred leading to the formation of corresponding transition metal－salicylideneimine complexes ML2 (M = Cu, Co, Ni, and Pd; L = S3PY, ClS3PY, and OMeS3PY). These reactions are monitored by UV-vis and fluorescence spectra. On the other hand, the reactions of [ZnL2] with AgNO3 revealed that the Ag+ ion did not replace the Zn2+ ion but directly bound to the 3-pyridine group of the [ZnL2] complexes as supported by 1H-NMR, MS, and element analysis. The reaction of Cu(S3py)2 or Ni(ClS3py)2, 2,6-naphthalenedicarboxylic acid (H2NDC), Zn(NO)3 or Zn(BF4)2, pyridind and DMAc under hydro(solovo)thermal conditions afforded two two-dimensional porous coordinstion polymers [Cu2(NDC)2(py)2]n and [Ni2(NDC)2(py)2]n, respectively .Both polymers are highly thermal stable ( >330℃), and can (almost) retain their crystallines after removing coordinated pyridine moleoules. In addition, both polymers are capables of adsorbing small solvent molecules such as pyridine, CH3CN, and water as confirmed by powder X-ray diffraction,thermogravimetric analysis, and element analysis.[[note]]碩