Theoretical investigations of Fe porphyrins. V. Low-lying electronic states of bisammineporphinatoiron(III)

Ab initio CI calculations are reported on the lowest doublet, quartet, and sextet states of [Fe^III(P)(NH₃)₂]⁺. The low-spin ground state is calculated as (d_xy² (d_π)³ with d_xy(d_π)⁴ higher by 0.15 eV. The near-ir bands at ～1 eV observed in low-spin ferriheme proteins are attributed to (π → d_π) transitions. The lowest high-spin state is ⁶A_1g, and the near-ir transitions of the high-spin ferriheme proteins observed at ～1.2 eV are attributed to higher ⁶[tripsextet] excited states [i.e., ring triplet, metal sextet]. The 30-ps “triplet” transient populated with low quantum yield observed in laser-flash studies on Fe^III(TPP)CI [TPP = tetrapbenylporphyrin] may be an ¹[tripsextet] state.     

Porphyrins

Extended Hückel calculations are reported for tetravalent porphin complexes of Si(OH)₂, Ge(OH)₂, GeCl₂, and SnCl₂ and divalent complexes of Ge, Sn, and Pb. Divalent Ge porphin is expected to be planar and have the extra two electrons in the ring. Divalent Sn and Pb porphins are expected to be non-planar and have the extra two electrons on the metal. The possibility of a charge transfer transition a ₁(p _z )e _g ^* () is noted, and its identication in available spectra of Sn and PbTPP is made. The electronic structure of the tetravalent species is similar to other metalloporphyrins except for the possibility of low lying ligand to porphin charge transfer states in the hydroxy complexes.

---

Zusammenfassung Für die vierwertigen Porphin-Komplexe des Si(OH)₂, Ge(OH)₂, GeCl₂ und SnCl₂ und die zweiwertigen Komplexe des Ge, Sn und Pb werden Berechnungen nach der erweiterten Hückel-methode durchgeführt. Von dem zweiwertigen Ge-Porphin wird erwartet, da\ es planar ist und da\ sich die beiden zusÄtzlichen Elektronen im Ring befinden, wÄhrend von den zweiwertigen Sn- und Pb-Porphinen zu erwarten ist, da\ sie nicht planar sind und die beiden zusÄtzlichen Elektronen sich am Metall befinden. Auf die Möglichkeit eines Charge-Transfer-übergangs a ₁(p _z )e _g ^* () wird hingewiesen, und dieser übergang wird in gemessenen Spektren von Sn und PbTPP identifiziert. Die Elektronenstruktur der vierwertigen Verbindung ist denjenigen anderer Metallporphyrine Ähnlich, au\er der Möglichkeit niedrig liegender Ligand-Porphin-Charge-Transfer-ZustÄnde in den Hydroxy-Komplexen.

---

Résumé Calculs de type Hückel étendu pour des complexes tétravalents de la porphine avec Si(OH)₂, Ge(OH)₂, GeCl₂ et SnCl₂ et des complexes divalents avec Ge, Sn et Pb. La porphine de Ge divalente est prévue plane avec les deux électrons supplémentaires dans le cycle. Les porphines divalentes de Sn et Pb sont prévues non planes avec les deux électrons supplémentaires sur le métal. On remarque la possibilité d'une transition de transfert de charge a ₁(p _z)e _g ^* () et on l'identifie dans les spectres disponsibles pour Sn et PbTPP. La structure électronique des espèces tétravalentes est semblable à celle des autres métalloporphyrines à l'existence possible près dans les complexes hydroxy d'états de transfert de charge de basse énergie entre le ligand et la porphine.

---

---

Paper XX: Ake, R. L, Gouterman, M.: Theoret. chim. Acta (Berl.) 17, 408–416 (1970).     

Porphyrins

The extended Hückel model is applied to porphyrin systems with metals Mn, Fe, Co, Ni, Cu, Zn and to the diprotic acid. A single method for choosing parameters is detailed. The model is used to discuss magnetic state, coupling of ring and metal, electronic transitions, and the effect of non-planarity.

---

Zusammenfassung Die erweiterte Hückel Theorie wird auf das Porphyrin-System mit den Metallen. Mn, Fe, Co, Ni, Cu und Zn sowie auf die zweifach protonierte Säure angewendet. Die Parameter werden dabei einheitlich gewählt. Anhand dieses Modells werden magnetische Eigenschaften, Kopplung zwischen Ring und Metall, Elektronenübergänge und der Einfluß der Abweichung von planarer Anordnung diskutiert.

---

Résumé Le modèle étendu de Hückel est appliqué aux complexes du porphyrine avec les métaux Mn, Fe, Co, Ni, Cu et Zn, et à l'acide diprotonique. On présente en détail une méthode unifiée pour obtenir les paramètres. L'état magnétique, le couplage cycle-métal, les transitions électroniques et l'effet de la non-planeïté sont discutés à l'aide de ce modèle.

---

---

National Institutes of Health Pre-Doctoral Fellow.     

Theoretical invstigations of the electronic states of porphyrins. I. Basis set development and predicted spectrum of pyrrole

A new minimum basis set was developed for use in computing excitation energies of large molecules. It is particularly suited to calculating ionization potentials and Rydberg transitions. Pyrrole excitation energies and oscillator strengths calculated with this basis set are compared to larger basis set ab initio and semiempirical results. The 6-eV band in the experimental spectrum is predicted to be the result of three Rydberg absorptions, with no underlying (π, π*) absorption. The calculations also provide an explanation for the observed N? H stretch in the 6-eV region.     

Effect of metal and substituents on the quasi-line spectra of some metalloporphyrins

Absorption spectra are reported for a number of metalloporphyrins in n-octane. For ZnP and PdP, sharp quasi-lines with linewidths ≈4 cm^?1 are observed at 15 and 35 K, respectively. The narrowest linewidths for PtP are ≈12 cm at 15 K, while NiP and CuP show no quasi-linear structure. In these latter cases, quasi-linewidth is attributed to electronic radiationless decay of the visible excited state. The various vibronic bands within Q(1, 0) are tabulated. The quasi-line structures for several zinc porphyrins at 77 K are also reported. Generally, these are not as sharp as those found in ZnP; in particular, Zn tetraphenyl porphin shows no quasi-linear structure. In these cases, the quasi-line structure is attributed to inhomogeneous broadening.     

Absorption and emission of thin solid films of octaethylporphin

Absorption and emission spectra at room temperature and emission spectra atliquid nitrogen temperature are reported for thin solid films of free base octaethylporphin. The room temperature visible absorption spectrum resembles that of the solution, except all four peaks show a red shift of ≈ 12 nm and all except the farthest red are broadened. The Soret band in the near UV is greatly broadened in the film, and its peak absorbance is substantially reduced. The room-temperature emission of the films is quite similar to that of solution fluorescence, except for a red-shift of ≈ 10 nm. But at low temperature two new peaks appear at 657 and 672 nm. Their intensity as a function of temperature can be explained by a simple exciton trapping model.     

Porphyrin films — 5: Strong fluorescence

Films of tetra(perfluorophenyl)porphyrin (TFPP) show comparable strong host fluorescence whether deposited on room temperature or heated (135°C) mica substrates. Films of tetraphenylporphyrin (TPP) show only 9% as much fluorescence when deposited on unheated mica but 60% as much fluorescence when deposited on heated mica; moreover, the latter films show enhanced fluorescence from impurity guests. Octaethylporphyrin (OEP) behaves like tetraphenylporphyrin. It is observed that crystallite size is larger for films deposited on heated as compared to unheated mica. Larger crystallites could explain increased host and guest fluorescence in films of TPP and OEP prepared on heated substrates if grain boundaries serve as sites both for quenching and for trapping host excitons. The strong host fluorescence of films of TFPP can be explained either (a) by very slow exciton diffusion rates or (b) very few host quenching sites and very few guest trapping sites.     

Calorimetric, photometric and lifetime determinations of fluorescence yields of fluorescein dyes

Abstract— The fluorescence yields and lifetimes of fluorescein and nine brominated derivatives in basic ethanol are reported. Calorimetric. photometric, and lifetime methods are used independently to measure the yields. A new and simple calorimetric method is presented for this purpose, and the accuracy of the techniques is assessed. There is good agreement between the calorimetric and photometric results. The importance of parameters such as purity, pH, and fluoresence reabsorption is illustrated. The theoretical determination of the natural radiative lifetime from the absorption spectrum is shown to have inherent ambiguities, so that only calorimetric methods provide a reliable, independent check for photometric yield measurements.     

Contrasting picosecond photokinetics of CoII and CoIII porphyrins verify excited-state predictions

Using picosecond transient absorption techniques, we have different low-lying excited states for several Co^II and Co^III porphyrins. These differences are interpreted in terms of theoretical calculations that predict the lowest-energy excited states to be ²(π·d) in Co^II and ³(d, d) in Co^III.