AgCrP2S6 reveals a momentum‐indirect band edge (≈1.35 eV) and chain‐locked linear dichroism: the first direct transitions emerge at 1.6–1.8 eV for E||a. Resonant Raman and photoemission corroborate this assignment. In ACPS/graphene heterostructures, photocurrent turns on above ≈1.5 eV and follows the same polarization selection rules (anisotropy ≈0.53),
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