{'fraction_non_alphanumeric': 0.04910179640718563, 'fraction_numerical': 0.015568862275449102, 'mean_word_length': 5.578740157480315, 'pattern_counts': {'":': 0, '<': 0, '<?xml version=': 0, '>': 0, 'https://': 0, 'lorem ipsum': 0, 'www.': 0, 'xml': 0}, 'pii_count': 0, 'substrings_counts': 0, 'word_list_counts': {'cursed_substrings.json': 0, 'profanity_word_list.json': 0, 'sexual_word_list.json': 0, 'zh_pornsignals.json': 0}}
Strongly coupled cyclometalated ruthenium-triarylamine hybrids: tuning electrochemical properties, intervalence charge transfer, and spin distribution by substituent effects.

Nine cyclometalated ruthenium complexes with a redox-active diphenylamine unit in the para position to the RuC bond were prepared. MeO, Me, and Cl substituents on the diphenylamine unit and three types of auxiliary ligands-bis(N-methylbenzimidazolyl)pyridine (Mebip), 2,2':6',2''-terpyridine (tpy), and trimethyl-4,4',4''-tricarboxylate-2,2':6',2''-terpyridine (Me3 tctpy)--were used to vary the electronic properties of these complexes. The derivative with an MeO-substituted amine unit and Me3 tctpy ligand was studied by single-crystal X-ray analysis. All complexes display two well-separated redox waves in the potential region of +0.1 to +1.0 V versus Ag/AgCl, and the potential splitting ranges from 360 to 510 mV. Spectroelectrochemical measurements show that these complexes display electrochromism at low potentials and intense near-infrared (NIR) absorptions. In the one-electron oxidized form, the complex with the Cl-substituted amine unit and Mebip ligand shows a moderate ligand-to-metal charge transfer at 800 nm. The other eight complexes show asymmetric, narrow, and intense intervalence charge-transfer transitions in the NIR region, which are independent of the polarity of the solvent. The Mebip-containing complexes display rhombic or broad isotropic EPR signals, whereas the other seven complexes show relatively narrow isotropic EPR signals. In addition, DFT and time-dependent DFT studies were performed to gain insights into the spin distributions and NIR absorptions.