Controlled self-assembly and photovoltaic characteristics of porphyrin derivatives on a silicon surface at solid–liquid interfaces

Abstract

Two meso-tetraphenylporphyrin (H2TPP) derivatives with different central metal ions, namely ZnTPP, CuTPP, were synthesized, and characterized by a series of spectroscopic methods. Their self-assembly behaviors in mixed solvents without surfactant were systematically investigated. The morphology of the thus produced nanoarchitectures could be efficiently controlled. Nanoslices can be manufactured when a volume of cyclohexane is involved, octahedrons can be produced when a mixed solvent of chloroform and isopropanol is employed, while four-leaf clover-shaped structures can be produced with a large volume of methanol injected. The nanostructures have been characterized by electronic absorption, scanning electron microscopy (SEM) and photoelectric conversion techniques. The internal structures of the nanostructures are well described by XRD. The nanostructures exhibit a power conversion under illumination intensity of 2.3 mW cm(-2). The present result appears to represent an effort toward controlling the morphology of self-assembled nanostructures of porphyrin derivatives via synthesis through introduction of metal-ligand and solvent interaction. Nevertheless, the fundamental study will be helpful to understand photoinduced energy/charge transport in an organic interface and this might also serve as promising building blocks for nanoscale power sources for potential application in solar energy technologies and organic electronics and optoelectronics.

Photoinitiated charge separation in a hybrid titanium dioxide metalloporphyrin peptide material

“…In the absence of peptide following the above sample preparation, (DPP)Zn in 100 mM NH 4 OH yields a very broad spectrum: split B-band (l max ¼ 415, 476 nm) and Q-band (l max ¼ 558, 590 nm). A broad red-shifted spectrum signifies aggregation [40][41][42] . (DPP)Zn (25 mM) in the presence of the assembled c16-AHL 3 K 3 -CO 2 H and c16-AHL 3 K 9 -CO 2 H (125 mM) in 100 mM NH 4 OH yields a sharp spectrum typical of histidyl axial coordination B-band (l max ¼ 426 nm) and Q-bands (l max ¼ 554, 592 nm).…”

Morphology‐Controlled Self‐Assembly of an Organic/Inorganic Hybrid Porphyrin Derivative Containing Polyhedral Oligomeric Silsesquioxane (POSS)

“…Additionally, for H 2 TPP‐POSS in pure n ‐hexane, the UV/Vis absorption bands continue to blueshift. The results indicate that H‐type aggregates exist between porphyrin rings in both the mixture of n ‐hexane/CHCl 3 and pure n ‐hexane 7. For H 2 TPP‐POSS in a mixture of MeOH/CHCl 3 , the spectrum shows similar changes to that of H 2 TPP‐POSS in a mixture of n ‐hexane/CHCl 3 (Figure 6 B).…”

“…A typical sample of H 2 TPP is a nonaggregated molecule with a typical electronic absorption spectrum in CHCl 3 with a Soret band at λ =418 nm and Q absorption bands at λ =517, 551, 590, and 646 nm 5d. 7 However, from the results given in Figure 4 A, the absorption spectrum of H 2 TPP‐POSS in CHCl 3 has a clear shoulder at λ =376 nm, which indicates a typical “face‐to‐face” stacking mode (H‐type aggregate) between porphyrin moieties with a planar construction 6. Additionally, with increasing concentration, both the Soret and Q absorption bands broaden; moreover, the absorption intensity at λ =418 nm does not increase linearly with concentration at concentrations over 6.6×10 −6 M (inset of Figure 4 A), which indicates that π–π stacking occurs between porphyrin moieties.…”

“…Cai et al. constructed two typical metalloporphyrins of zinc and copper tetrakisphenyl porphyrin (ZnTPP and CuTPP, respectively), and found that different solvents and the introduction of different ions into the porphyrin central hole led to different nanostructures 7. Additionally, Aida et al.…”

Thermodynamic study of the interaction between 5,10,15,20-tetrakis-(N-methyl-4-pyridyl)porphyrin tetraiodine and sodium dodecyl sulfate

“…Among a wide variety of assembly strategies [10], surfactant-assisted self-assembly has received a considerable attention [11]. By taking into account that aggregation of porphyrins, in the presence of surfactants, can be driven by non-covalent interactions, such as hydrophobic-hydrophobic, π-π stacking between the molecules [12], or by electrostatic ones [13], it can be possible to manage to produce micro-or nano-structures with different supramolecular organizations, different sizes and shapes [10,14,15], allowing the designing of new optical materials for photocatalytic [16], photovoltaic [17] and light harvesting [12] system applications.…”