雙Salamo型3d、3d-2s和3d-4f金屬配合物的合成、晶體結(jié)構(gòu)與光譜性質(zhì)
發(fā)布時(shí)間:2018-06-02 02:30
本文選題:salamo配體 + 三核配合物; 參考:《蘭州交通大學(xué)》2016年碩士論文
【摘要】:在結(jié)構(gòu)方面,肟類配合物由對(duì)稱演變到不對(duì)稱,由同核到異核,由單肟到雙肟再到多肟,且合成方法多種多樣。在諸多領(lǐng)域中,多肟類配體及其配合物有著極為可觀的應(yīng)用價(jià)值,其中,多肟類大環(huán)配合物在催化反應(yīng)、半導(dǎo)體、熒光材料及生物等領(lǐng)域中有著重要作用,這是由于其中心離子的磁自旋交換作用,使金屬配合物具有了非線性光學(xué)性質(zhì)與良好的磁性質(zhì)。本論文中,設(shè)計(jì)并成功合成了一種新型雙salamo型四肟配體H4L,該化合物通過(guò)元素分析、核磁氫譜以及紅外光譜等表征方法,確定其即為目標(biāo)產(chǎn)物。然后,通過(guò)與金屬離子配位得到:[LZn_3(OAc)_2(CH_3OH)_2]?3CHCl_3(1),[LZn_2Ca(OAc)_2]?CHCl_3(2),[LZn_2Sr(OAc)_2](3),[LZn_2Ba(OAc)_2(CH_3OH)]?CHCl_3(4),[LZn_2La(OAc)_3](5),[LZn_2Ce(OAc)_3](6),[LZn_2Dy(OAc)_3(CH_3OH)]?CH_2Cl_2(7)。制備7種配合物后,分別通過(guò)元素分析、紅外光譜及紫外滴定實(shí)驗(yàn),對(duì)其結(jié)構(gòu)進(jìn)行了表征。最終,使用X-射線單晶衍射儀收集晶體學(xué)數(shù)據(jù),解析數(shù)據(jù)并深入研究了其空間結(jié)構(gòu)。分別測(cè)定了配合物的激發(fā)譜與發(fā)射譜,對(duì)其光學(xué)性質(zhì)進(jìn)行了初步探究。配合物1:化學(xué)組成為C_(41)H_(45)Cl_9N_4O_(16)Zn_3,Mr=1364.97,屬于單斜晶系,空間群P21/n,晶胞參數(shù):a=14.0480(4)?,b=16.5494(3)?,c=23.6735(5)?,β=100.464(2)°,Z=4,V=5412.2(2)?3,R1=0.0519,wR2=0.1136;配合物2:化學(xué)組成為C_(37)H_(35)CaCl_3N_4O_(14)Zn_2,Mr=1036.86,屬于三斜晶系,空間群`P1,晶胞參數(shù):a=13.4794(7)?,b=13.6682(6)?,c=15.4156(9)?,a=85.483(4)°,β=65.228(5)°,γ=65.053(5)°,Z=2,V=2321.6(2)?3,R1=0.0524,wR2=0.1549;配合物3:化學(xué)組成為C_(36)H_(34)N_4O_(14)SrZn_2,Mr=965.03,屬于三斜晶系,空間群`P1,晶胞參數(shù):a=12.6197(14)?,b=13.346(2)?,c=15.6864(18)?,a=114.099(13)°,β=104.696(10)°,γ=99.435(11)°,Z=2,V=2223.2(6)?3,R1=0.0690,wR2=0.0926;配合物4:化學(xué)組成為C_(39)H_(43)BaCl_3N_4O_(16)Zn_2,Mr=1198.20,屬于三斜晶系,空間群`P1,晶胞參數(shù):a=10.6854(5)?,b=14.1383(7)?,c=16.2738(13)?,a=73.657(6)°,β=88.178(5)°,γ=78.971(4)°,Z=2,V=2315.0(2)?3,R1=0.0520,wR2=0.1453;配合物5:化學(xué)組成為C_(38)H_(37)LaN_4O_(16)Zn_2,Mr=1075.36,屬于三斜晶系,空間群`P1,晶胞參數(shù):a=10.4562(4)?,b=14.5979(7)?,c=18.4521(7)?,a=73.452(4)°,β=75.215(3)°,γ=77.263(4)°,Z=2,V=2577.05(19)?3,R1=0.0353,wR2=0.0787;配合物6:化學(xué)組成為C_(38)H_(37)CeN_4O_(16)Zn_2,Mr=1076.57,屬于三斜晶系,空間群`P1,晶胞參數(shù):a=13.4231(12)?,b=13.5379(12)?,c=15.6521(13)?,a=64.689(9)°,β=78.336(8)°,γ=70.323(8)°,Z=2,V=2415.4(4)?3,R1=0.0717,wR2=0.1441;配合物7:化學(xué)組成為C_(40)H_(43)Cl_2DyN_4O_(17)Zn_2,Mr=1215.92,屬于單斜晶系,空間群P21/c,晶胞參數(shù):a=12.6510(3)?,b=13.6894(3)?,c=26.8174(7)?,β=103.515(3)°,Z=4,V=4515.77(19)?3,R1=0.0402,wR2=0.1044。
[Abstract]:In terms of structure, the complexes of oxime evolved from symmetry to asymmetry, from homonuclear to heteronuclear, from single oxime to dioxime to polyoxime. In many fields, polyoxime ligands and their complexes have great application value. Among them, polyoxime macrocyclic complexes play an important role in catalytic reactions, semiconductors, fluorescent materials and biology, etc. This is due to the magnetic spin exchange of the central ions, which makes the metal complexes have nonlinear optical properties and good magnetic properties. In this paper, a novel double salamo tetraoxime ligand H4L was designed and synthesized successfully. The compound was identified as the target product by elemental analysis, NMR and IR spectra. 鐒跺悗,閫氳繃涓庨噾灞炵瀛愰厤浣嶅緱鍒,
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