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The bifunctional organic ions containing carboxyl groups as spacer cations will form additional hydrogen bonding between perovskite layers, resulting in higher stability of the material. The band gaps of these materials vary from 2.19 to 2.6 eV depending on the octahedral connection mode and [PbI6]4- octahedral distortion level, density functional theory calculations (DFT) are consistent with our experimental trends and suggest that the face-sharing structure has the maximum band gap due to its flatter electron band structure. Bright gr