Zinc Tetraphenylporphyrin Molecules Research Articles

Coadsorption of ZnTPP and 2HMCTPP on Rutile TiO2(110).

Pure zinc tetraphenylporphyrin (ZnTPP) adsorbs on rutile TiO2(110) as flat-lying molecules, mostly interacting with the surface through weak van-der-Waals interactions. Pure monocarboxyphenyl triphenylporphyrin (2HMCTPP) forms a covalent bond to the rutile TiO2(110) surface through the carboxylic acid group, yielding densely-packed layers of upright-standing molecules. If given the chance, 2HMCTPP could therefore be expected to displace the weaker-bonding ZnTPP molecules. However, if 2HMCTPP is deposited on top of a ZnTPP layer, a coadsorption structure instead forms, with the carboxylic-acid groups of the 2HCMTPP molecules bonding to titanium atoms of the surface exposed by gaps between the molecules in the flat-lying ZnTPP adsorption structure.

Controlled Self‐Assembly of Zn–Tetraphenylporphyrins for Efficient Photocatalytic Solar H2 Production and Simultaneous Organic Transformation to Valuable Chemicals

Herein, we have designed aqueous dispersed self‐assembled nanostructures with diverse morphologies from the zinc tetraphenyl porphyrin (ZnTPP) monomer employing a simple solution‐based coprecipitation methods. Detail morophological studies have been carried out by various electron microscopy techniques. Finally, the structural features were correlated with the underpinning photophysical processes using steady‐state and time‐resolved spectroscopy. Detailed studies suggest that control morphology and highly defined intermolecular interactions affect the overall photoinduced charge transfer process. Based on the fundamental investigations, all these different types of nanostructures have been utilized as photocatalysts for solar hydrogen production, without using any cocatalysts, and it was found that the spherical nanostructure exhibits significantly higher H2 production rates of ~1682 m mole/ g, which is few folds higher than other 1D and 2D nanostructured materials. The experimental findings were further supported by the TD‐DFT study. Furthermore, the detailed computational studies suggest that the spherical aggregates exhibited a more vital interaction between the ZnTPP molecules, causes significant electronic coupling between bright local excited and charge transfer states, which supports our experimental findings. Finally, we have selectively utilized the oxidative half‐reaction for the simultaneous transformation of glycerol to valuable chemicals along with photocatalytic H2 production through reductive half‐reaction.

Revealing the morphology and the magnetic properties of single buried cobalt-ZnTPP hybrid interfaces by ferromagnetic nuclear resonance spectroscopy

The deeply buried, yet most important part of any spintronic device is the interface. This is even more interesting and much more complex when soft, light materials like organic molecules are in contact with an inorganic metallic electrode. Hence, exceptional care is required to better understand the phenomena driven by this type of organic/inorganic interfaces. To this end, ferromagnetic nuclear resonance (FNR) spectroscopy studies were performed to investigate the morphology and the magnetic properties of the hybrid organic-inorganic interfaces when zinc tetraphenyl porphyrin (ZnTPP) molecules are at the vicinity of ferromagnetic metallic cobalt (Co) layers. The FNR experimental results show that when ZnTPP is deposited on top of Co the resulting interface is smoother and sharper compared to the more extended interface obtained when Co is deposited on top of ZnTPP. The shape of the spectra suggests that no chemical bonds take place between the interfacial Co atoms and the ZnTPP molecules and that interactions at the interfaces are governed by weak van der Waals forces. Finally, FNR also showed that the magnetic anisotropy at the Co-ZnTPP hybrid interfaces is reduced compared to the magnetic anisotropy of the Co atoms inside the Co films.

Nanoscale integration of porphyrin in GroEL protein cage: Photophysical and photochemical investigation.

In this paper, we introduce a new type of functional, supramolecular porphyrin conjugate created using the bacterial GroEL protein cage based on non-specific hydrophobic interaction. The synthesis, structure and property of the porphyrin conjugate were characterized by dynamic light scattering, UV-vis spectroscopy and fluorescence spectroscopy. We observed that the model zinc-tetraphenylporphyrin (Zn-TPP) with high hydrophobicity can be well-dispersed in aqueous solutions with the aid of GroEL open chamber, which is known to be a favorable nanocompartment for aggregation-prone molecules. The maximal encapsulation efficiency of Zn-TPP in GroEL was determined to be ~98%. It is further seen that the constructed double Zn-TPP-GroEL complex exhibited good photocatalytic activity in the model reactions of the production of singlet oxygen and the reduction of methyl viologen under illumination with visible light. Moreover, we found that GroEL can significantly improve the photostability of Zn-TPP molecules as a result of nanoscale assembly within its hydrophobic chamber. Hence enhanced water solubility and photostability of Zn-TPP, which are considered as the first two hurdles for the wide usage of porphyrins, were achieved simultaneously by the development of GroEL cage as a building block. Supramolecular nanostructures formed from porphyrins (or related molecules) and GroEL for photocatalysis would greatly simplify applications of such structures.

Local structure and morphological evolution of ZnTPP molecules grown on Fe(001)-p(1 × 1)O studied by STM and NEXAFS

When used as substrates, thin metal-oxide (MO) layers can perturb the physical and chemical properties of molecules in contact with the surface. To study the molecule-MO layer interaction, we focused our investigation on a prototypical interface, namely zinc tetraphenylporphyrin (ZnTPP) film on Fe(001)-p(1 × 1)O. In a previous study, we found that no significant change of the electronic structure takes place at the monolayer (ML) coverage either in the core level photoemission spectra or in the highest occupied molecular orbitals (HOMOs). However, molecules showed the occurrence of a commensurate (5 × 5) diffraction pattern that indicates a certain degree of interaction with the substrate. In order to better understand the effective molecule/metal decoupling operated by the FeO layer, we performed a combined investigation based on a scanning tunneling microscopy (STM) study of the self-assembled ZnTPP molecular layer and on a near edge X-ray absorption fine structure spectroscopy (NEXAFS).Molecules are found to lie almost parallel to the substrate, even if the central macrocycle displays a characteristic small saddle-like distortion (<15°). The corresponding reduction of the molecular symmetry from D4h to D2h drives the azimuthal orientation with respect to the substrate and determines the co-existence of four equivalent (5 × 5) ZnTPP domains, following the substrate four-fold symmetry. The comparison with films of increasing thickness shows that, beyond the second layer, the molecules gradually tilt-off the surface (by at least 40°) ordering into 3D islands. The NEXAFS resonances of the lowest unoccupied orbitals (LUMOs) do not display significant changes from the monolayer to the multilayer thickness range, apart from minor modification of the LUMOs relative intensity. The latter variation may be associated with the change of spatial spread of the molecular orbitals in the contact layer due to the saddle-like distortion.

Enhanced electron transfer ability via coordination in block copolymer/porphyrin/fullerene micelle

Inspired by structures of antenna-reaction centers in photosynthesis, the complex micelle was prepared from zinc tetra-phenyl porphyrin (ZnTPP), fullerene derivative (PyC60) and poly(ethylene glycol)-block-poly(e-caprolactone) (PEG-b-PCL). The core-shell structure made the hydrophobic donor-acceptor system work in aqueous. In micellar core, coordination interaction occurred between ZnTPP and PyC60 molecules which ensured the enhanced energy migration from the donor to the acceptor. The enhanced interaction between porphyrin and fullerene was confirmed by absorption, steady-state fluorescence and transient fluorescence. The generation of singlet oxygen and superoxide radical was detected by iodide method and reduction of nitro blue tetrazolium, respectively, which confirmed that electron transfer reaction in the complex micellar core occurred. Moreover, the complex micelle exhibited effective electron transfer performance in photodebromination of 2,3-dibromo-3-phenylpropionic acid. The complex micellar structure endowed the donor-acceptor system with improved stability under irradiation. This strategy could be helpful for designing new electron transfer platform and artificial photosynthetic system.

Charge-induced distortion and stabilization of surface transfer doped porphyrin films

The interaction between zinc-tetraphenylporphyrin (ZnTPP) and fullerenes (C60 and C60F48) are studied using ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling microscopy (STM). Low temperature STM reveals highly ordered ZnTPP monolayers on Au(111). In contrast to C60, a submonolayer coverage of C60F48 results in long-range disorder of the underlying single ZnTPP layer and distortion of individual ZnTPP molecules. This is induced by substantial charge transfer at the organic-organic interface, revealed by the interface energetics from UPS. However, a second layer of ZnTPP prevents C60F48 guests from breaking the self-assembled porphyrin template. This finding is important for understanding the growth behaviour of "bottom-up" functional nanostructures involving strong donor-acceptor heterojunctions in molecular electronics.

Aging-induced optical anisotropy in thermally grown thin ZnTPP films on Si

We present reflection anisotropy spectroscopy (RAS) as a powerful optical technique for degradation studies of structurally changing thin organic films, here the case of porphyrin films. The measured optical anisotropy of a thin (d = 16 nm) ZnTPP (Zinc tetraphenylporphyrin) film grown by thermal evaporation on silicon using reflectance anisotropy spectroscopy was studied before and after aging in ambient conditions. The observed absorption features, also found by standard transmission spectroscopy, are correlated with the π–π* electronic transitions of the Q and Soret bands of the molecule. Simulation of RAS spectra revealed blue-shifted resonances, which are in agreement with a preferential face-to-face (stacking) arrangement of the ZnTPP molecules. The findings are in agreement with atomic force microscopy studies of the surface morphology showing with aging a transition from a closed film to separated aggregates.

Dye−Host Interactions for Local Effects Recognition in Homogeneous and Nanostructured Media

Steady-state absorption and emission as well as time-resolved fluorescence spectra of NR (nile red) and ZnP (zinc tetraphenylporphyrin) were studied in a variety of solvents. All spectra were decomposed as a sum of Gaussian bands, and the spectral shifts found were analyzed in terms of the general solvatochromic theory. Ground state permanent dipoles, electronic spectra, and Onsager cavity radii were obtained for each dye in several solvents using intermediate neglect of differential overlap (INDO) software provided by ArgusLab. ZnP emission spectra also reveal the presence of a new band interpreted as due to an excitonic coupling between pairs of weakly interacting ZnP molecules. The center to center distance in these excitonic pairs was estimated. Studies were extended to the system ZnP−PVP (PVP refers to poly(vinylpyridine)), and its photophysical properties were determined. NR and ZnP were also incorporated into rigid matrixes of PS (polystyrene), PVP, SiO2, and TiO2. NR in these rigid media probes local polarities and enables the estimation of the effective dielectric constant of the matrixes. The behavior of ZnP emission when incorporated in the same rigid media was also analyzed. In particular, in PS and TiO2 matrixes, the spectra were interpreted as the result of an excitonic coupling between pairs of porphyrin molecules and according to Kasha's theory the center to center distance between the interacting molecules could be estimated. The ZnP−SiO2 emission spectrum is ascribed to monomeric porphyrin, while in the ZnP−PVP matrix the emission spectrum was interpreted in terms of two distinct emitting states.

Luminescence of Zinc Tetraphenylporphyrin in Ethylene Glycol-in-Oil Microemulsions

Photophysical properties of zinc-tetraphenylporphyrin (ZnTPP) were studied in n-heptane/AOT/ethylene glycol and isooctane/AOT/ethylene glycol microemulsions. Results of steady state and transient fluorescence techniques show the existence of different spectroscopic ZnTPP species located at different environments of the reverse micelles. The behavior of such species depends on the molar ratio [ethylene glycol]/[AOT]. Upon addition of ethylene glycol to the medium, a large displacement of ZnTPP molecules from the apolar bulk to the polar phase takes place due to the existence of a “strong” interaction between the polar solvent and the Zn metal ion (solvation type). The equilibria of ZnTPP between the different environments was quantified from absorption and emission spectra.