Krätschmer Frederic, Gui Xin, Gamer Michael T, Klopper Wim, Roesky Peter W
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstr. 15, 76131 Karlsruhe, Germany.
Institute of Physical Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 2, 76131 Karlsruhe, Germany.
Dalton Trans. 2022 Apr 5;51(14):5471-5479. doi: 10.1039/d1dt03795a.
Dinuclear gold(I) compounds are of great interest due to their aurophilic interactions that influence their photophysical properties. Herein, we showcase that gold-gold interactions can be influenced by tuning the electronic properties of the ligands. Therefore, various substituted (R) ,'-bis(2,6-dimethylphenyl)formamidinate ligands (RXylForm; Xyl = 2,6-dimethylphenyl and Form = formamidinate) were treated with Au(tht)Cl (tht = tetrahydrothiophene) to give salt metathesis the corresponding gold(I) compounds [RXylFormAu] (R = -OMe, -Me, -Ph, -H, -SMe, and -COMe). All complexes showed intense luminescence properties at low temperatures. Alignment with the Hammett parameter revealed the trends in the H and C NMR spectra. These results showed the influence of the donor-acceptor abilities of different substituents on the ligand system which were confirmed with calculated orbital energies. Photophysical investigations showed their lifetimes in the millisecond range indicating phosphorescence processes and revealed a redshift with the decreasing donor ability of the substituents in the solid state.
双核金（I）化合物因其影响光物理性质的亲金相互作用而备受关注。在此，我们展示了金-金相互作用可通过调节配体的电子性质来影响。因此，用Au(tht)Cl（tht = 四氢噻吩）处理各种取代的（R），'-双（2,6-二甲基苯基）甲脒配体（RXylForm；Xyl = 2,6-二甲基苯基，Form = 甲脒），通过盐复分解反应得到相应的金（I）化合物[RXylFormAu]（R = -OMe、-Me、-Ph、-H、-SMe和-COMe）。所有配合物在低温下均表现出强烈的发光性质。与哈米特参数的比对揭示了氢谱和碳谱中的趋势。这些结果表明了不同取代基的给体-受体能力对配体体系的影响，这一点通过计算的轨道能量得到了证实。光物理研究表明它们的寿命在毫秒范围内，表明存在磷光过程，并揭示了在固态中随着取代基给体能力的降低出现红移。
