Publication Details (including relevant citation information):
Adinehnia, Morteza, Mazur, Ursula, Hipps, K. W. Crystal Growth & Design 2014 14 (12) 6599-6606
Abstract: Crystallization of a binary porphyrin nanostructure (BPN) of TSPP (meso-tetra(4-sulfonatophenyl)porphyrin) and TMPyP (meso-tetra(N-methyl-4-pyridyl)porphyrin) was studied. The morphology and crystallinity of the BPN was investigated using transmission electron (TEM) and atomic force microscopies (AFM). The composition of the BPN was analyzed using X-ray photoelectron spectroscopy (XPS), elemental analysis, and UV–visible spectroscopy. These techniques revealed a 1:1 composition of anionic to cationic porphyrins in the structure. Our initial studies on the synthesis of these materials revealed that the average size of these crystals increases monotonically with synthesis temperature and decreasing monotonically with initial concentration (supersaturation) of the mother solution. In this work we have developed a model to simulate the growth of these organic monocrystalline materials for the first time. This model encompasses all the major kinetic and thermodynamic steps of crystallization including homogeneous nucleation, growth, and Ostwald ripening. The model is then validated by comparing the simulation results with experimental crystallization histograms. The unknown parameters are extracted by fitting the simulation to the experimental data. This investigation will help in better understanding of crystallization and size control in this class of photoactive organic materials. The integration rate constant pre-exponential is found to be (2.9 ± 1.3) × 106 m4/(mol s), and the activation energy for the integration rate is determined as 44 ± 2 kJ/mol.
Address (URL): http://dx.doi.org/10.1021/cg501506s