کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
9763691 | 1498848 | 2005 | 6 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Photochemical reactions of rhodium(III) diimine complexes in solid glycerol matrices
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی معدنی
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چکیده انگلیسی
At temperatures below 150Â K in rigid glycerol glasses [Rh(CN)2(s-NN)2]PF6 complexes display a 3ÏÏ* â gs phosphorescence characteristic of the s-NN ligand [s-NNÂ =Â 1,10-phenanthroline (phen), 4-Mephen, 4,7-Me2phen, and 3,4,7,8-Me4phen]. Above 150Â K but below the melting point of glycerol a temperature-dependent first-order reaction occurs upon irradiation with UV light. The temperature dependences of these photochemical reactions conform to the Arrhenius equation with an activation energy range of 2000-2500Â cmâ1, which is a range averaging 725Â cmâ1 lower than that previously reported for [Rh(s-NN)3](PF6)3 complexes. These results are interpreted in terms of the thermal redistribution of energy from an unreactive 3ÏÏ* excited term to a close-lying chemically reactive 3dd level that has been lowered in energy with respect to that of the corresponding [Rh(s-NN)3](PF6)3 complex. The relationships of the Arrhenius activation energies to the electronic structures of the parent complexes and to the natures of the products are discussed.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Coordination Chemistry Reviews - Volume 249, Issues 13â14, July 2005, Pages 1310-1315
Journal: Coordination Chemistry Reviews - Volume 249, Issues 13â14, July 2005, Pages 1310-1315
نویسندگان
J.A. Brozik, G.A. Crosby,