Tetrakis(thiadiazole)porphyrazines.: 4.: Direct template synthesis, structure, general physicochemical behavior, and redox properties of AlIII, GaIII, and InIII complexes
Tetrakis(thiadiazole)porphyrazines.: 4.: Direct template synthesis, structure, general physicochemical behavior, and redox properties of AlIII, GaIII, and InIII complexes
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DOI：
10.1021/ic050866b
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发表时间：
2005-11-14
影响因子：
4.6
通讯作者：
Stuzhin, PA
中科院分区：
文献类型：
--
作者：
Donzello, MP;Agostinetto, R;Stuzhin, PA
四元单核苷酸衍生物（1，2，5-噻二唑）四氮杂卟啉，[TTDP zH（2）），其主族三价金属离子具有下式[TTDPzMX]（TTDPz =四（1，2，5-噻二唑）四氮杂卟啉阴离子; M = Al-III，X = Cl-，Br-，OH-; M = Ga-III，X = Cl-，OH-; M = In-III，X = AcO-）的合成，并通过单晶X射线衍射、红外光谱、紫外-可见光谱、循环伏安和光谱电化学等手段对其进行了研究。在MX3盐（M = Al-III，Ga-III; X = Cl-，Br-）存在下，3，4-二氰基-1，2，5-噻二唑的前体在热喹啉中通过直接自环四聚反应得到配合物[TTDPzMX]（M = Al-III，X = Cl-，Br-; M = Ga-III，X = Cl-），并水解得到相应的氢氧化物衍生物[TTDPzMOH]。在CH_3COOH中，由大环[TTDP_zH（2）]与In（OH）（OAc）（2）反应得到In-III配合物[TTDP_zIn（OAc）]。在173 K下对两种同构物种[TTDPzMCl]进行了单晶X射线研究。（M = Al-III，Ga-III），空间群为P（1）/bar，a = 12.470（14），B = 12.464（13），c = 13.947（12）埃，α = 70.72（3），β = 79.76（3），对于[TTDP zAICI]，γ = 90.06（3）度，V = 2009.3（3）埃（3），Z = 4，a = 12.429（3），B 12.430（3），c = 13.851（3）埃，α = 70.663（6），β = 79.788（8），γ = 89.991（9）度，对于[TTDP zGaCl]，V = 1983.3（7）埃（3），Z = 4。在Mill中心附近存在四方锥配位，Cl-占据顶点位置（Al-Cl = 2.171（5）和Ga-Cl = 2.193（1）埃）。Al-III和Ga-III位于距N-4系统中心0.416（6）和0.444（2）埃的距离处。分子堆积由堆叠的双层组成，内部和外部的平均层间距分别为3.2和3.3埃。IR光谱显示[TTDPzAlCl]在345 cm（-1）处的v（Al-Cl），[TTDPzAlBr]在330 cm（-1）处的v（Al-Br），以及[TTDPzGaCl]在382 cm（-1）处的v（Ga-Cl）。在弱碱性溶剂（吡啶、DMF、DMSO）和酸性溶剂（CF_3COOH、H_2SO_4）中的紫外-可见光谱在Sorel（300-400 nm）和Q-带区域（640-660 nm）显示出典型的强烈的pi -> pi* 跃迁带，这些带证明索马依赖于溶剂的性质，特别是在酸性溶液中。循环伏安法，差分脉冲伏安法，和薄层光谱电化学测量在吡啶和二甲基甲酰胺的物种[TTDPzMX]表明可逆的第一和第二个单电子还原，而额外的不明确的减少观察到更多的负电位。由于TTDPz大环具有显著的吸电子特性，其中含有成环的强缺电子噻二唑环，因此所研究的物种比其酞菁或卟啉类似物更容易还原。
Monometallic derivatives of tetrakis(1,2,5-thiadiazole)porphyrazine, [TTDPzH(2)), with main group tervalent metal ions having the formulae (TTDPzMX] (TTDPz = tetrakis(1,2,5-thiadiazole)porphyrazinato dianion; M = Al-III, X = Cl-, Br-, OH-; M = Ga-III, X = Cl-, OH-; M = In-III, X = AcO-) were prepared and investigated by single-crystal X-ray analysis and IR and UV-vis spectroscopy as well as cyclic voltammetry and spectroelectrochemistry. The complexes [TTDPzMX] (M = Al-III, X = Cl-, Br-; M = Ga-III, X = Cl-) were obtained by direct autocyclotetramerization of the precursor 3,4-dicyano-1,2,5-thiadiazole in hot quinoline in the presence of MX3 salts (M = Al-III, Ga-III; X = Cl-, Br-) and were hydrolized to form the corresponding hydroxide derivatives, [TTDPzMOH]. The In-III complex, [TTDPzln(OAc)], was obtained from the free-base macrocycle [TTDPzH(2)] with ln(OH)(OAc)(2) in CH3COOH. A single-crystal X-ray study was made at 173 K on the two isostructural species [TTDPzMCl] (M = Al-III, Ga-III), which have space group P (1) over bar, with a = 12.470(14), b = 12.464(13), and c = 13.947(12) angstrom, alpha = 70.72(3), beta = 79.76(3), and gamma = 90.06(3)degrees, V = 2009.3(3) angstrom(3), and Z = 4 for [TTDPzAICI] and a = 12.429(3), b 12.430(3), and c = 13.851(3) angstrom, alpha = 70.663(6), beta = 79.788(8), and gamma = 89.991(9)degrees, V = 1983.3(7) angstrom(3), and Z = 4 for [TTDPzGaCl]. Square pyramidal coordination exists about the Mill centers, with Cl- occupying the apical position (Al-Cl = 2.171(5) and Ga-Cl = 2.193(1) angstrom). Al-III and Ga-III are located at distances of 0.416(6) and 0.444(2) angstrom from the center of the N-4 system. The molecular packing consists of stacked double layers with internal and external average interlayer distances of 3.2 and 3.3 angstrom, respectively. IR spectra show v(Al-Cl) at 345 cm(-1) for [TTDPzAICI], v(Al-Br) at 330 cm(-1) for [TTDPzAlBr], and v(Ga-Cl) at 382 cm(-1) for [TTDPzGaCI]. The UV-vis spectra in weakly basic (pyridine, DMF, DMSO) and acidic solvents (CF3COOH, H2SO4) show the typical intense pi -> pi* transition bands in the Sorel (300-400 nm) and Q-band regions (640-660 nm), the bands evidencing soma dependence on the nature of the solvent, particularly in acidic solutions. Cyclic voltammetry, differential pulse voltammetry, and thin-layer spectroelectrochemical measurements in pyridine and dimethylformamide of the species [TTDPzMX] indicate reversible first and second one-electron reductions, whereas additional ill-defined reductions are observed at more negative potentials. The examined species are much easier to reduce than their phthalocyanine or porphyrin analogues as a result of the remarkable electron-attracting properties of the TTDPz macrocycle which contains annulated strongly electron-deficient thiadiazole rings.