d‐Orbital Reconstructions Forced by Double Bow‐Shaped Deformations and Second Coordination Sphere Effects of Cu(II) Heme Analogs in HER**

Abstract

Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes (4‐, 3‐, 2‐ and 1‐Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis‐ortho) to give double bow‐shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d‐orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1‐Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow‐shaped architecture and the strong saddle porphyrin core in 1‐Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation.