N^N^C-Cyclometalated rhodium(<scp>iii</scp>) complexes with isomeric pyrimidine-based ligands: unveiling the impact of isomerism on structural motifs, luminescence and cytotoxicity
作者:Sofia N. Vorobyeva、Sof'ya A. Bautina、Nikita A. Shekhovtsov、Elena B. Nikolaenkova、Taisiya S. Sukhikh、Yuliya A. Golubeva、Lyubov S. Klyushova、Viktor P. Krivopalov、Marianna I. Rakhmanova、Christophe Gourlaouen、Mark B. Bushuev
DOI:10.1039/d4dt00824c
日期:——
pyrimidine-based ligands and their rhodium(III) complexes with regard to their structures and properties was investigated. Two isomeric ligands, 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2,5-diphenylpyrimidine (HL2,5) and 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2,6-diphenylpyrimidine (HL2,6), were synthesized. The ligands differ by the degree of steric bulk: the molecular structure of HL2,5 is more distorted due to
研究了嘧啶基配体及其铑( III )配合物的异构现象对其结构和性能的影响。两个异构配体,4-(3,5-二甲基-1 H -吡唑-1-基)-2,5-二苯基嘧啶 ( HL 2,5 ) 和 4-(3,5-二甲基-1 H -吡唑-1合成了-yl)-2,6-二苯基嘧啶( HL 2,6 )。配体的空间体积程度有所不同:由于嘧啶环的相邻位置 4 和 5 上存在吡唑基和苯基, HL 2,5的分子结构更加扭曲。 HL 2,5和HL 2,6与 RhCl 3的络合导致 sp 2 C–H 键活化,从而分离出两个络合物: [RhL 2,5 (Solv)Cl 2 ]· n EtOH和[ RhL 2,6 (Solv)Cl 2 ]· n EtOH (Solv = H 2 O, EtOH),具有吡唑基嘧啶分子的去质子化形式,其将Rh 3+离子配位为N^N^C-三齿配体。 根据DFT模型,去质子化的机制涉及(i)2-苯基中的C