Stagni Stefano, Palazzi Antonio, Zacchini Stefano, Ballarin Barbara, Bruno Carlo, Marcaccio Massimo, Paolucci Francesco, Monari Magda, Carano Maurizio, Bard Allen J
Dipartimento di Chimica Fisica ed Inorganica, Università di Bologna, viale Risorgimento 4, I-40136 Bologna, Italy.
Inorg Chem. 2006 Jan 23;45(2):695-709. doi: 10.1021/ic0514905.
A new family of mono- and dinuclear ruthenium polypyridyl complexes containing 5-aryltetrazolate ligands such as the deprotonated form of 4-(1H-tetrazol-5-yl)benzonitrile (4-TBNH) and bis(1H-tetrazol-5-yl)benzene (BTBH(2)) have been synthesized and thoroughly characterized. The reactivity of the mononuclear species toward different electrophiles such as H(+) and CH(3)(+) has been investigated, and the effects of the resulting regioselective electrophilic attacks on the electronic and structural properties of the tetrazolate ligand have been studied by NMR ((1)H, (13)C) spectroscopy and X-ray crystal structures. Absorption and emission spectroscopy, together with an electrochemical and UV-vis-NIR spectroelectrochemical investigation of the uncoordinated ligand and complexes, has been performed, highlighting a rather good luminescence efficiency and a poor bridge-mediated electronic communication between the metal centers of the dinuclear complexes. The electrogenerated chemiluminescence (ECL) of the dinuclear species has been explored, and for one of these, an exceptionally high ECL efficiency has been observed, comparable to that of Ru(bpy)(3), which is considered a standard in ECL studies.
已合成并全面表征了一个新的含有5-芳基四唑配体的单核和双核钌多吡啶配合物家族，如4-(1H-四唑-5-基)苯甲腈（4-TBNH）的去质子化形式和双(1H-四唑-5-基)苯（BTBH(2)）。研究了单核物种对不同亲电试剂如H(+)和CH(3)(+)的反应性，并通过NMR（(1)H、(13)C）光谱和X射线晶体结构研究了由此产生的区域选择性亲电攻击对四唑配体电子和结构性质的影响。对未配位配体和配合物进行了吸收和发射光谱以及电化学和紫外-可见-近红外光谱电化学研究，突出了双核配合物相当好的发光效率以及金属中心之间较差的桥介导电子通讯。已探索了双核物种的电致化学发光（ECL），其中之一观察到了异常高的ECL效率，与Ru(bpy)(3)相当，Ru(bpy)(3)被认为是ECL研究中的标准。
