Design of oxophilic metalloporphyrins: an experimental and DFT study of methanol binding†,Dalton Transactions

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Design of oxophilic metalloporphyrins: an experimental and DFT study of methanol binding†
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-08-01 00:00:00 , DOI: 10.1039/c8dt02432d
Sandra Olsson _{1,

2,

3,

4} , Christian Dahlstrand _{1,

2,

3,

4} , Adolf Gogoll _{1,

2,

3,

4}

Affiliation

By systematic measurements we have evaluated a series of tetraphenyl metalloporphyrins and halogenated tetraphenyl metalloporphyrin derivatives for binding to ligands with oxygen containing functional groups, using methanol, acetic acid and acetone as examples. Experimental binding constants identified three metalloporphyrins with good binding to all three ligands: MgTPFPP, MgTPPBr₈ and ZnTPPBr₈ as well as a range of porphyrins binding to select ligands. Based on these results the optimal porphyrins can be selected for the desired binding interactions. We also show how to use DFT calculations to evaluate the potential binding between a metalloporphyrin and a ligand, which is deduced from free energies of binding ΔG, charge transfer ΔQ, and change of metal spin state. Computations on unsubstituted porphyrins in lieu of tetraphenyl porphyrin systems yield reliable predictions of binding interactions with good correlation to the corresponding experimental data. The calculations have also yielded interesting insights into the effect of halogenation in the β-position on the binding to ligands with oxygen containing functional groups.

中文翻译：

嗜氧性金属卟啉的设计：甲醇结合的实验和DFT研究†

通过系统的测量，我们以甲醇，乙酸和丙酮为例，评估了一系列四苯基金属卟啉和卤代四苯基金属卟啉衍生物与具有含氧官能团的配体的结合。实验结合常数确定了与所有三个配体（MgTPFPP，MgTPPBr ₈和ZnTPPBr _8）具有良好结合的三种金属卟啉，以及一系列与所选配体结合的卟啉。基于这些结果，可以针对所需的结合相互作用选择最佳的卟啉。我们还展示了如何使用DFT计算来评估金属卟啉与配体之间的潜在结合，这是从结合自由能ΔG，电荷转移ΔQ推导而来的，以及金属自旋状态的变化。代替四苯基卟啉体系的未取代卟啉的计算可得出结合相互作用的可靠预测，并与相应的实验数据具有良好的相关性。该计算还产生了关于β位卤化对与含氧官能团的配体结合的影响的有趣见解。

更新日期：2018-08-01

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