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.