Tailored D‐π Conjugation Boosts Piezocatalytic CO ₂ Reduction in a Platinum(II)‐Acetylide Framework

ABSTRACT Piezocatalytic CO ₂ reduction offers a sustainable route for converting mechanical energy into chemical fuels. However, its practical implementation demands catalysts that concurrently exhibit a strong piezoelectric response and high catalytic activity. Herein, we report a one‐pot synthesis of well‐defined metal–acetylide frameworks (TTED‐M‐AFs; M = Pt, Pd, Ni) incorporating M ^II (PEt ₃ ) ₂ units into an extended graphdiyne‐type scaffold via robust ─C≡C─M ^II (PEt ₃ ) ₂ ─C≡C─ linkages. These molecular metal‐bis(acetylide) motifs function as intrinsic active sites for CO ₂ reduction. Under mechanical agitation, the Pt ^II ‐based framework achieves a CO production rate of 72.03 µmol g ⁻¹ h ⁻¹ with 92.4% selectivity, outperforming its Pd ^II and Ni ^II analogues by factors of 1.17 and 1.73, respectively—a trend consistent with their piezoelectric coefficients ( d ₃₃ = 35, 21.9, and 12.5 pm V ⁻¹ ). Combined experimental and theoretical analyses reveal that the piezoelectric field in TTED‐Pt‐AF enhances CO ₂ adsorption and promotes local electron accumulation, thereby lowering the activation energy barrier. Furthermore, in situ high‐pressure FT‐IR spectroscopy demonstrates that the Pt ^II ‐bis(acetylide) centers exhibit superior electronic synergy with the tetraphenylene‐derived π‐conjugated matrix under mechanical stress, inducing pronounced d–π orbital hybridization. The exceptional piezocatalytic performance, coupled with a scalable synthesis, underscores the promise of metal–acetylide frameworks as efficient platforms for mechano‐driven CO ₂ valorization.