Polarizable Anionic Sublattices Can Screen Molecular Dipoles in Noncentrosymmetric Inorganic–Organic Hybrids

We report the growth and photophysical characterization of two polar hybrid lead halide phases, methylenedianiline lead iodide and bromide, (MDA)Pb₂I₆ and (MDA)Pb₂Br₆, respectively. The phases crystallize in noncentrosymmetric space group Fdd2, which produces a highly oriented molecular dipole moment that gives rise to second harmonic generation (SHG) upon excitation at 1064 nm. While both compositions are isostructural, the size dependence of the SHG signal suggests that the bromide exhibits a stronger phase-matching response whereas the iodide exhibits a significantly weaker non-phase-matching signal. Similarly, fluorescence from (MDA)Pb₂Br₆ is observed around 630 nm below 75 K whereas only very weak luminescence from (MDA)Pb₂I₆ can be seen. We attribute the contrasting optical properties to differences in the character of the halide sublattice and postulate that the increased polarizability of the iodide ions acts to screen the local dipole moment, effectively reducing the local electric field in the crystals.