Raïch Panisello Ot, Jover Jesús, Puigjaner Cristina, Ferrer Montserrat, Martínez Manuel
Secció de Química Inorgànica, Departament de Química Inorgànica i Orgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, 08028 Barcelona, Spain.
Inorg Chem. 2024 Sep 2;63(35):16251-16263. doi: 10.1021/acs.inorgchem.4c02169. Epub 2024 Aug 21.
A series of square-planar palladium and platinum compounds with -blocking phosphanes and terminal azobenzene ligands M(dppp)(azo) (azo = CN(CH)-N═N-(CH)CN (), CN(CH)-N═N-(CH) ()) and {M(tpbz)}(azo) (azo = CN(CH)-N═N-(CH) ()) have been synthesized and fully characterized. Similarly to the uncoordinated ligands, the new coordination compounds have shown to be photochemically active with respect to their trans-to-cis isomerization process. Their cis-to-trans back spontaneous reaction have been studied as a function of solvent, temperature and pressure and the corresponding activation parameters determined in order to investigate the mechanism of these transformations. The results obtained are indicative of the operation of a rotational mechanism with no cooperativity between the azo ligands attached to the same metal. Density functional theory calculations have been carried out in order to estimate the relative energies of the different photoisomers for the theoretical interpretation of the experimental data.
一系列具有位阻膦和末端偶氮苯配体的平面正方形钯和铂化合物M(dppp)(azo)（azo = CN(CH)-N═N-(CH)CN ()，CN(CH)-N═N-(CH) ()）以及{M(tpbz)}(azo)（azo = CN(CH)-N═N-(CH) ()）已被合成并全面表征。与未配位的配体类似，新的配位化合物在其反式到顺式异构化过程中表现出光化学活性。已研究了它们顺式到反式的自发逆向反应作为溶剂温度和压力的函数，并确定了相应的活化参数，以研究这些转化的机制。所得结果表明存在一种旋转机制，且连接在同一金属上的偶氮配体之间不存在协同作用。已进行密度泛函理论计算，以估计不同光异构体的相对能量，用于对实验数据进行理论解释。
