Hydrogen bonds and steric effects induced structural modulation of three layered iodoplumbate hybrids from nonperovskite to perovskite structure.

Directed by diprotonated organic diamines containing both primary and tertiary ammonium groups, three layered iodoplumbate hybrids, {[H2DMPDA][PbI4]}n (1), {[H2DEPDA]4[Pb5I18]}n (2) and {[H2TMEDA][Pb3I8]}n (3) (DMPDA = N,N-dimethyl-1,3-propanediamine, DEPDA = N,N-diethyl-1,3-propanediamine, TMEDA = N,N,N',N'-tetramethylethylenediamine), have been synthesized solvothermally. 1 presents a layered perovskite structure based on corner-sharing PbI6 octahedra, compound 2 consists of a Pb4I20 perovskite motif and a Pb2I10 dimeric motif and compound 3 comprises Pb3I13 units connected by face-sharing and edge-sharing modes. Structural modulations from nonperovskite to perovskite structure are strongly correlated to steric effects and hydrogen bonding interaction at the organic-inorganic interface. Band gaps for 1-3 , estimated as 2.21, 2.58 and 2.73 eV, respectively, also reveal an interesting correlation with structural modulation, and the red shift for 1 is attributed to large Pb-I(equatorial)-Pb bond angles.