Enhanced yield-mobility products in hybrid halide Ruddlesden-Popper compounds with aromatic ammonium spacers.

Hybrid halide Ruddlesden-Popper compounds are related to three-dimensional hybrid AMX3 perovskites (e.g. where A is a monovalent cation, M is a divalent metal cation, and X is a halogen) with the general formula L2An-1MnX3n+1 where L is a monovalent spacer cation. The crystal structure comprises perovskite-like layers separated by organic cation spacers. Here two Ruddlesden-Popper compounds with a conjugated cation, 2-(4-biphenyl)ethylammonium (BPEA) prepared by solvothermal and solvent evaporation techniques are reported. The structures of the two compounds: (BPEA)2PbI4 and (BPEA)2(CH3NH3)Pb2I7, were solved by X-ray crystallography. The aromatic rings of the BPEA groups are well-separated in the organic layers leading to optical properties comparable to n = 1 and 2 hybrid halide Ruddlesden-Popper compounds with simpler alkyl ammonium cations. The ambient stability of both compounds over time was also confirmed by powder X-ray diffraction. Finally, the transient photoconductance, measured by time-resolved microwave conductivity, show that the compounds have maximum yield-mobility products respectively of 0.07 cm2 V-1 s-1 and 1.11 cm2 V-1 s-1 for (BPEA)2PbI4 and (BPEA)2(CH3NH3)Pb2I7, both slightly enhanced over what has been measured for compounds with n-butylammonium spacer cations.

Advances in Guanidine Ligand Design: Synthesis of a Strongly Electron-Donating, Imidazolin-2-iminato Functionalized Guanidinate and its Properties on Iron.

Imidazolin-2-imines (ImRN-), derived from N-heterocylic carbenes, have been shown to be strong electron donors when directly coordinated to metals or when used as a substituent in larger ligand frameworks. In an attempt to enhance the electron-donating properties of the popular guanidine ligand class, the effect of appending an ImRN- backbone onto a guanidinate scaffold was investigated. Addition of 1 equiv of [Li(Et2O)][Im tBuN] to the aryl carbodiimide (dippN)2C (dipp = 2,6-diisopropylphenyl) cleanly affords the lithium Im tBuN-functionalized guanidinate [Li(THF)2][(Im tBuN)C(Ndipp)2] (1). Subsequent metalation of the ligand with FeBr2 gives the yellow Fe(II) complex {[(Im tBuN)C(Ndipp)2]FeBr}2 (4) in good yield. Solid-state structural analyses of both 1 and 4 shows the Im tBuN- group acts as a non-coordinating backbone substituent. Direct structural comparison of 4 to the closely related guanidinate and ketimine-guanidinate complexes {[(X)C(Ndipp)2]FeBr}2 (X = t Bu2C=N (5); N( i Pr)2 (6)), differing only in their backbone, reveals a detectable resonance contribution of the Im tBuN- group to the guanidinate ligand electronic structure. Moreover, the Fe(II)/Fe(III) redox couple of 4 (E1/2 = -0.67 V) is cathodically shifted by greater than 200 mV from the oxidation potentials of 5 (E1/2 = -0.42 V) and 6 (E1/2 = -0.45 V), demonstrating the [(Im tBuN)C(Ndipp)2]- system to be a quantifiably superior electron donor.