9. Complexes between core-modified porphyrins ZnP(X)4 (X = P and S) and small semiconductor nanoparticle Zn6S6: are they possible?
-
Aleksey E. Kuznetsov
Abstract
The synthetic approach of the anchoring of porphyrins to the surface of semiconductor nanoparticles (NPs) has been realized to form very promising organic/inorganic nanocomposites. They have been of considerable scientific and a wide practical interest including such areas as material science, biomedical applications,and dye-sensitized solar cells (DSSCs). Macrocyclic pyrrole-containing compounds, such as phthalocyanines and porphyrins, can bind to the NP surface by a variety of modes: as monodentate ligands oriented perpendicular to the NP surface, parallel to the NP surface, or, alternatively, in a perpendicular orientation bridging two adjacent NPs. Also, non-covalent (coordination) interactions may be realized between the NP via its metal centers and appropriate meso-attached groups of porphyrins. Recently, we showed computationally that the prominent structural feature of the core-modified MP(X)4 porphyrins (X = P) is their significant distortion from planarity. Motivated by the phenomenon of numerous complexes formation between tetrapyrrols and NPs,we performed the density functional theory (DFT) studies of the complex formation between the core-modified ZnP(X)4 species (X = P and S) without any substituents or linkers and semiconductor NPs, exemplified by small NP Zn6S6. The complexes formation was investigated using the following theoretical approaches: (i) B3LYP/6-31G* and (ii) CAM-B3LYP/6-31G*, both in the gas phase and with implicit effects from C6H6 considered. The calculated binding energies of the complexes studied were found to be significant, varying from ca. 29 up to ca. 69 kcal/mol, depending on the complex and the approach employed.
Abstract
The synthetic approach of the anchoring of porphyrins to the surface of semiconductor nanoparticles (NPs) has been realized to form very promising organic/inorganic nanocomposites. They have been of considerable scientific and a wide practical interest including such areas as material science, biomedical applications,and dye-sensitized solar cells (DSSCs). Macrocyclic pyrrole-containing compounds, such as phthalocyanines and porphyrins, can bind to the NP surface by a variety of modes: as monodentate ligands oriented perpendicular to the NP surface, parallel to the NP surface, or, alternatively, in a perpendicular orientation bridging two adjacent NPs. Also, non-covalent (coordination) interactions may be realized between the NP via its metal centers and appropriate meso-attached groups of porphyrins. Recently, we showed computationally that the prominent structural feature of the core-modified MP(X)4 porphyrins (X = P) is their significant distortion from planarity. Motivated by the phenomenon of numerous complexes formation between tetrapyrrols and NPs,we performed the density functional theory (DFT) studies of the complex formation between the core-modified ZnP(X)4 species (X = P and S) without any substituents or linkers and semiconductor NPs, exemplified by small NP Zn6S6. The complexes formation was investigated using the following theoretical approaches: (i) B3LYP/6-31G* and (ii) CAM-B3LYP/6-31G*, both in the gas phase and with implicit effects from C6H6 considered. The calculated binding energies of the complexes studied were found to be significant, varying from ca. 29 up to ca. 69 kcal/mol, depending on the complex and the approach employed.
Chapters in this book
- Frontmatter I
- Preface V
- Contents VII
- List of Contributing authors XIII
- 1. Optical properties of monolayer BeC under an external electric field: A DFT approach 1
- 2. Theoretical investigation of the derivatives of favipiravir (T-705) as potential drugs for Ebola virus 19
- 3. Potential thermally activated delayed fluorescence properties of a series of 2,3-dicyanopyrazine based compounds 33
- 4. γ-Al2O3:Ce3+Cu2+ as a phosphor material; DFT+U and experimental approach 49
- 5. A DFT perspective analysis of optical properties of defected germanene mono-layer 65
- 6. DFT studies on storage and adsorption capacities of gases on MOFs 83
- 7. Metastability of the boron-vacancy complex in silicon: Insights from hybrid functional calculations 113
- 8. Molecular structure and vibrational spectra of 2-(4-bromophenyl)-3-(4-hydroxyphenyl) 1,3-thiazolidin-4-one and its selenium analogue: Insights using HF and DFT methods 123
- 9. Complexes between core-modified porphyrins ZnP(X)4 (X = P and S) and small semiconductor nanoparticle Zn6S6: are they possible? 135
- 10. DFT computations on vibrational spectra: Scaling procedures to improve the wavenumbers 147
- 11. Substituent effects on linear and nonlinear optical properties of fluorescent (E)-2-(4-halophenyl)-7- arlstyrylimidazo[1,2-A] pyridine: spectroscopic and computational methods 193
- Index 229
Chapters in this book
- Frontmatter I
- Preface V
- Contents VII
- List of Contributing authors XIII
- 1. Optical properties of monolayer BeC under an external electric field: A DFT approach 1
- 2. Theoretical investigation of the derivatives of favipiravir (T-705) as potential drugs for Ebola virus 19
- 3. Potential thermally activated delayed fluorescence properties of a series of 2,3-dicyanopyrazine based compounds 33
- 4. γ-Al2O3:Ce3+Cu2+ as a phosphor material; DFT+U and experimental approach 49
- 5. A DFT perspective analysis of optical properties of defected germanene mono-layer 65
- 6. DFT studies on storage and adsorption capacities of gases on MOFs 83
- 7. Metastability of the boron-vacancy complex in silicon: Insights from hybrid functional calculations 113
- 8. Molecular structure and vibrational spectra of 2-(4-bromophenyl)-3-(4-hydroxyphenyl) 1,3-thiazolidin-4-one and its selenium analogue: Insights using HF and DFT methods 123
- 9. Complexes between core-modified porphyrins ZnP(X)4 (X = P and S) and small semiconductor nanoparticle Zn6S6: are they possible? 135
- 10. DFT computations on vibrational spectra: Scaling procedures to improve the wavenumbers 147
- 11. Substituent effects on linear and nonlinear optical properties of fluorescent (E)-2-(4-halophenyl)-7- arlstyrylimidazo[1,2-A] pyridine: spectroscopic and computational methods 193
- Index 229
