Non-Templated Assembly of D5h-Symmetric Pd5L10 Rings by Precise Ligand Angle Adjustment

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Abstract

We report a series of Pd(II)nL2n coordination rings for which nuclearity is controlled by the binding angle of the corresponding bis-monodentate bridging ligands. Judicious choice of the angle within a family of rather rigid ligands allowed for the first-time to synthesize a homoleptic five-membered Pd5L10 ring that does not require any template to form. We demonstrate that control over the ring size is maintained both in the solid-, solution-, and gas-phase. Two X-ray structures of five-membered rings from ligands with ideal angles (yielding a perfect pentagonal ring) vs. suboptimal angles (resulting in a highly distorted structure) illustrate the importance of the correct ligand geometry. A mathematical model for estimating the expected ring size based on the ligand angle was derived and DFT computations show that ring-strain is the major factor determining the assembly outcome.

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Neukirch, L., Kulas, M. D., Holstein, J. J., & Clever, G. H. (2024). Non-Templated Assembly of D5h-Symmetric Pd5L10 Rings by Precise Ligand Angle Adjustment. Chemistry - A European Journal, 30(27). https://doi.org/10.1002/chem.202400132

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