Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, IN, 47405, USA.
Angew Chem Int Ed Engl. 2017 Oct 9;56(42):13083-13087. doi: 10.1002/anie.201707869. Epub 2017 Sep 13.
The acid-base switching of complexes formed from anti-electrostatic anion-anion homodimers of organophosphates and cyanostar macrocycles was investigated for the first time. High-fidelity 2:2 complexes were selected by using suitably sized organo substituents. Reversible and direct switching occurs with triflic acid and hydroxide base. An unexpected acid⋅⋅⋅anion heterodimer was discovered with weaker picric acid, which helped reveal some of the elementary steps. Switching can also proceed in a cooperative (strong anion then weak acid) or stepwise manner (weak acid then strong anion).
首次研究了由有机膦酸盐和蓝星大环形成的反静电阴离子-阴离子同二聚体的配合物的酸碱转换。通过使用合适大小的有机取代基选择了高保真 2:2 配合物。三氟甲磺酸和氢氧化物碱可实现可逆和直接的转换。与较弱的苦味酸形成了意想不到的酸⋅⋅⋅阴离子杂二聚体，这有助于揭示一些基本步骤。转换也可以通过协同（强阴离子然后弱酸）或分步（弱酸然后强阴离子）方式进行。
