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Electronic Structure of Anilinopyridinate-Supported Ru25+ Paddlewheel Compounds
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-11-15 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02557 Amanda R. Corcos 1 , Michael D. Roy 1 , Michelle M. Killian 1 , Stephanie Dillon 1 , Thomas C. Brunold 1 , John F. Berry 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-11-15 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02557 Amanda R. Corcos 1 , Michael D. Roy 1 , Michelle M. Killian 1 , Stephanie Dillon 1 , Thomas C. Brunold 1 , John F. Berry 1
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The electronic structures of the diruthenium compounds Ru2(ap)4Cl (1, ap = 2-anilinopyridinate) and Ru2(ap)4OTf (2) were investigated with UV–vis, resonance Raman, and magnetic circular dichroism (MCD) spectroscopies; SQUID magnetometry; and density functional theory (DFT) calculations. Both compounds have quartet spin ground states with large axial zero-field splitting of ∼60 cm–1 that is characteristic of Ru25+ compounds having a (π*, δ*)3 electron configuration and a Ru–Ru bond order of ∼2.5. Two major visible absorption features are observed at ∼770 and 430 nm in the electronic spectra, the assignments of which have previously been ambiguous. Both bands have significant charge-transfer character with some contributions from d → d transitions. MCD spectra were measured to enable the identification of d → d transitions that are not easily observable by UV–vis spectroscopy. In this way, we are able to identify bands due to δ → δ* and δ → π* transitions at ∼16 100 and 11 200–12 300 cm–1, respectively, the latter band being sensitive to the π-donating character of the axial ligand. The Ru–Ru stretches are coupled with pyridine rocking motions and give rise to observed resonance Raman peaks at ∼350 and 420 cm–1, respectively.
中文翻译：
苯胺吡啶鎓负载的Ru 2 5+桨轮化合物的电子结构
用紫外可见光谱，共振拉曼光谱和磁圆二色性（MCD）研究了钌化合物Ru 2（ap）4 Cl（1，ap = 2-苯胺基吡啶二酸酯）和Ru 2（ap）4 OTf（2）的电子结构。）光谱学; SQUID磁力计; 和密度泛函理论（DFT）计算。两种化合物都具有四重旋自旋态，轴向大的零场分裂约为60 cm –1，这是具有（π*，δ*）3的Ru 2 5+化合物的特征电子构型和Ru-Ru键序约为2.5。在电子光谱的约770和430 nm处观察到两个主要的可见光吸收特征，它们的分配以前是模棱两可的。这两个频带都具有显着的电荷转移特性，并具有d→d跃迁的贡献。对MCD光谱进行了测量，以鉴定d→d跃迁，而这些跃迁是紫外可见光谱法不易观察到的。这样，我们就能够识别出分别由δ→δ*和δ→π*跃迁引起的谱带，分别在〜16 100和11 200–12 300 cm –1处，后一个谱带对谱带的π捐赠特征敏感。轴向配体。Ru-Ru拉伸与吡啶的摇摆运动结合在一起，并在〜350和420 cm –1处产生观察到的共振拉曼峰。， 分别。
更新日期：2017-11-15
中文翻译：
苯胺吡啶鎓负载的Ru 2 5+桨轮化合物的电子结构
用紫外可见光谱，共振拉曼光谱和磁圆二色性（MCD）研究了钌化合物Ru 2（ap）4 Cl（1，ap = 2-苯胺基吡啶二酸酯）和Ru 2（ap）4 OTf（2）的电子结构。）光谱学; SQUID磁力计; 和密度泛函理论（DFT）计算。两种化合物都具有四重旋自旋态，轴向大的零场分裂约为60 cm –1，这是具有（π*，δ*）3的Ru 2 5+化合物的特征电子构型和Ru-Ru键序约为2.5。在电子光谱的约770和430 nm处观察到两个主要的可见光吸收特征，它们的分配以前是模棱两可的。这两个频带都具有显着的电荷转移特性，并具有d→d跃迁的贡献。对MCD光谱进行了测量，以鉴定d→d跃迁，而这些跃迁是紫外可见光谱法不易观察到的。这样，我们就能够识别出分别由δ→δ*和δ→π*跃迁引起的谱带，分别在〜16 100和11 200–12 300 cm –1处，后一个谱带对谱带的π捐赠特征敏感。轴向配体。Ru-Ru拉伸与吡啶的摇摆运动结合在一起，并在〜350和420 cm –1处产生观察到的共振拉曼峰。， 分别。
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