Mechanical and structural properties of ionically self-assembled nanostructures of meso-tetra(4-sulfonatophenyl)porphyrin (TSPP) and meso-tetra(4-pyridyl)porphyrin (TPyP) are presented. This is the first time that elastic modulus of an ionic porphyrin nanostructure has been reported. X-ray photoelectron spectroscopy (XPS), UV-visible spectra, and elemental analysis all support a stoichiometric 1 : 1 TSPP to TPyP composition. Atomic force microscopy (AFM) revealed that the porphyrin nanostructure is composed of stacked ribbons about 20 nm tall, 70 nm wide, and several microns in length. High resolution transmission electron microscopy (HRTEM) images showed clear lattice fringes 1.5 ± 0.2 nm in width aligned along the length of the nanorod. Selected area electron diffraction (SAED) and powder X-ray diffraction patterns of TSPP:TPyP are consistent with an orthorhombic system and space group Imm2 with lattice parameters a = 26.71 Å, b = 20.16 Å, and c = 8.61 Å. Crystallographic data is consistent with an arrangement of alternating face-to-face TSPP and TPyP molecules forming ordered columns along the length of the nanorods. The structural integrity of the solid is attributed to combined noncovalent interactions that include ionic, hydrogen bonding, and π–π interactions. The values of Young's modulus obtained for the crystalline TSPP:TPyP nanorods averaged 6.5 ± 1.3 GPa. This modulus is comparable to those reported for covalently bonded flexible polymeric systems. The robust bonding character of the TSPP:TPyP nanostructures combined with their mechanical properties makes them excellent candidates for flexible optoelectronic devices.

Porphyrins are fascinating molecules with applications spanning various scientific fields. In this review we present the use of periodic density functional theory (PDFT) calculations to study the structure, electronic properties, and reactivity of porphyrins on ordered two dimensional surfaces and in the formation of nanostructures. The focus of the review is to describe the application of PDFT calculations for bridging the gaps in experimental studies on porphyrin nanostructures and self-assembly on 2D surfaces. A survey of different DFT functionals used to study the porphyrin-based system as well as their advantages and disadvantages in studying these systems is presented.

We provide a structure–function relationship study of an organic crystalline photoconductor composed of oppositely charged ionic porphyrins. Nano to millimeter size crystals with well-defined morphology composed of stoichiometric amounts of meso-tetra(N-methyl-4-pyridyl)porphyrin (TMPyP) and meso-tetra(4-sulfonatophenyl)porphyrin (TSPP) were grown in a controlled and reproducible manner. The rod shaped TMPyP:TSPP monoclinic P2₁/c crystals have a pseudo-hexagonal cross section and their internal structure consists of highly organized molecular columns of alternating porphyrin cations and anions. Experimental characterization of the TMPyP:TSPP solid was performed using powder-XRD, AFM, SEM, DRS UV-visible, and photoconductivity measurements. For the first time the morphology of an ionic porphyrin solid is predicted. The TMPyP:TSPP crystals are non-conducting in the dark but become conductive with illumination. The n-type photoconductive response is significantly faster with excitation in the Q-band than with excitation in the Soret band. Quantum mechanical calculations were performed to determine the electronic band structure and density of states and to explain the photoconduction in TMPyP:TSPP. Based on these results we propose a model in which two types of photoconductivity occur: (1) band conduction which occurs at all excitation wavelengths and (2) hopping conductivity caused by metastable photoinduced defects that form primarily at higher energy excitations. This work combines the results from structural and theoretical studies and correlates them with electronic and optoelectronic properties thereby opening the road to the engineering of highly-organized functional materials from organic π-conjugated molecules.