Meyer Andreas, Abdullin Dinar, Schnakenburg Gregor, Schiemann Olav
Institute of Physical and Theoretical Chemistry, Rheinische Friedrich-Wilhelms-University Bonn, Wegelerstr. 12, 53115 Bonn, Germany.
Institute of Inorganic Chemistry, Rheinische Friedrich-Wilhelms-University Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
Phys Chem Chem Phys. 2016 Apr 7;18(13):9262-71. doi: 10.1039/c5cp07621h.
A rigid, nitroxide substituted terpyridine ligand has been used to synthesize hetero- and homoleptic bis-terpyridine complexes of copper(II). The homoleptic complex represents a three-spin system, while the metal ion in the heteroleptic complex is in average bound to one nitroxide bearing ligand. Both complexes are used as model systems for EPR distance measurements using pulsed electron-electron double resonance (PELDOR or DEER) and relaxation induced dipolar modulation enhancement (RIDME) sequences. The results of both methods are analyzed using detailed geometric data obtained from the crystal structure of the homoleptic complex as well as information concerning ligand scrambling and the electronic structure of the copper center. In addition, both methods are compared with respect to their sensitivity, the extent of orientation selectivity and the influence of multispin effects.
一种刚性的、氮氧化物取代的三联吡啶配体已被用于合成铜（II）的杂配和同配双三联吡啶配合物。同配配合物代表一个三自旋体系，而异配配合物中的金属离子平均与一个带有氮氧化物的配体结合。这两种配合物都被用作模型体系，用于使用脉冲电子 - 电子双共振（PELDOR或DEER）和弛豫诱导偶极调制增强（RIDME）序列进行电子顺磁共振（EPR）距离测量。使用从同配配合物的晶体结构获得的详细几何数据以及有关配体混乱和铜中心电子结构的信息，对这两种方法的结果进行了分析。此外，还比较了这两种方法在灵敏度、取向选择性程度和多自旋效应影响方面的差异。
