Institute of Crystallography - CNR

Molecular Design and Crystal Chemistry of Polyfluorinated Naphthalene-bis-phenylhydrazimides with Superior Thermal and Polymorphic Stability and High Solution Processability

Naphthalene tetracarboxylic diimides (NDIs) are highly promising air-stable n-type molecular semiconductor candidates for flexible and cost-effective organic solar cells and thermoelectrics. Nonetheless, thermal and polymorphic stabilities of environmentally stable NDIs in the low-to-medium temperature regime (<300 °C) remain challenging properties. Structural, thermal, spectroscopic, and computational features of polyfluorinated NDI-based molecular solids (with up to 14 F atoms per NDI molecule) are discussed upon increasing the fluorination level. Slip-stacked arrangement of the NDI cores with suitable ?-? stacking and systematically short interplanar distances (<3.2 Å) are found. All these materials exhibit superior thermal stability (up to 260 °C or above) and thermal expansion coefficients indicating a response compatible with flexible polymeric substrates. Optical bandgaps increase from 2.78 to 2.93 eV with fluorination, while LUMO energy levels decrease down to -4.37 eV, as shown per DFT calculations. The compounds exhibit excellent solubility of 30 mg mL in 1,4-dioxane and DMF.

Chemistry - A European Journal
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Abbinante, Vincenzo Mirco; Zambra, Marco; García-Espejo, Gonzalo; Pipitone, Candida; Giannici, Francesco; Milita, Silvia; Guagliardi, Antonietta; Masciocchi, Norberto
Authors IC CNR