中文摘要

本研究合成了Rh(bipy)(bzpy)Cl2 ( bipy = bipyridine，bzpy = ortho-C-deprotonated form of 2-benzoylpyridine )的混配基型不對稱錯合物，由元素分析、質譜、紅外光譜及核磁共振光譜鑑定組成及結構，判斷出其為cisβ型之異購物。
紅外光譜中，錯合物在1674cm-1位置的羰基振動吸收，可以判斷配位子bzpy是以N-C-型式與金屬鍵結，而非以N-O型式鍵結。
紫外-可見光方面，錯合物在39.2~31.2 kK之間有很強吸收峰 (ε>104 cm-1M-1)，推測應為配位子bzpy與bipy之ππ*過渡。而28.6 kK的中等強度(ε= 6.5×103 cm-1M-1)吸收帶，推測是配位到銠金屬bzpy之羰基吸收，屬於n→π*過渡。在25.0 kK含有肩帶微弱吸收亦皆延伸到可見光區，此區域吸收有可能是電荷轉移或 dd* 躍遷，由於和電荷轉移吸收互為重疊干擾，而無法清楚解析出。激發極化光譜中，於35.0及25.0kK處的轉折，推測其吸收型態可能非為單一。
在放光偵測上，於低溫77K，Me2SO溶劑中，在16.9 ~ 12.3kK 的能量範圍內，可偵測到寬廣、對稱且不具結構性之放光帶，其最大放光位置在 14.3kK ( 695 nm )，半生期約 58 μs 左右，推斷屬於 dd* 型態放光。在放光極化光譜，放光區呈現平坦、斜率趨近於零之曲線，表示為單一型態的放光。
電化學方面，結合脈衝伏安法(NPV)及定電位電解(CPE)之結果，推論出循環伏安法(CV)圖譜上的第一還原峰包含二個單電子的轉移過程，並伴隨氯離子脫去的化學反應。而第三還原峰由NPV中峰值電流比值以及加入phenol後的反應，認定是還原到bzpy羰基上之π*軌域的可逆單電子轉移過程。

英文摘要

In this research, the complex Rh(bipy)(bzpy) ( where bipy is bipyridine, bzpy is ortho-C-deportonated form of 2-benzoylpyridine ) has been synthesized, and characterized with MS, IR, and NMR spectra. The structure of the complex is assigned as cisβ form isomer.
The carbonyl absorption of bzpy of the complex, about 1674 cm-1 in IR spectrum, indicates N-C- bonding to metal Rh(Ⅲ), not N-O bonding .
The bands (39.2~31.2 kK) show ππ* transitions in ligands of the complex exhibit strong absorption in the UV region (ε＞104 cm-1M-1 ). The dd* absorptions (25.0kk) of center metal are convered with the charge transfer signal. It’s difficult to distinguish clearly between the two absorptions under the long tail.
The luminescence is found at 77K in Me2SO .It exhibits a broad, symmetric, structure less emission (16.9~12.3 kK) with 58 μｓlifetime .The maximum emission intensity is about 14.3kK.The luminescence is assigned as dd* phosphorescence. The emission polarization spectrum of this complex in emission region is a linear curve whose slope is closed to zero, indicates a single emission.
The cyclic voltammorgrams of the complex shows three reduction waves between 0~-1.8 V vs. SCE in 0.1 TEAP/Me2SO. The first peak is constituted by two electronics reduction steps followed by fast elemination of chlorides. In the addition of phenol, the third is suggested to be a reductive process that one electron transfer to π* orbital at carbonyl of bzpy.

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