Electronic spectra of copper and zinc complexes of porphyrins containing ethoxycarbonyl substituents

Copper and zinc complexes of porphyrins containing ethoxycarbonyl substituents have been synthesized and their absorption spectra in the visible region have been studied. A connection has been shown between the α/β ratio of the absorption bands and the order of substitution of electronegative groups in the porphyrins.

     

Syntheses and oxygenation of iron(II) “strapped” porphyrin complexes

A general route to ‘strapped’ porphyrins which are bridged between diagonally opposite meso-positions is described. Studies on the oxygenation and carbonylation of their iron(II) complexes have shown that they are inferior to ‘capped’ porphyrins as models for the oxygen-carrying haemoproteins. The results reported herein suggest that strapping structures which do not enforce well-defined and rigid cavities for oxygen binding afford little protection against irreversible oxidation of (dioxygen) (porphyrin) iron(II) complexes.     

Synthesis of Linear Amphipathic Porphyrin Dimers and Trimers: An Approach to Bilayer Lipid Membrane Spanning Porphyrin Arrays

A modular building-block approach has been developed for the construction of linear amphipathic porphyrin arrays. The reaction of meso-(trifluoromethyl)dipyrromethane and an aldehyde under the conditions of the two-step room temperature porphyrin synthesis affords the trans-substituted porphyrin (13-56% yields). A similar reaction with two different aldehydes provides access to porphyrins bearing two different functional groups. An ethyne porphyrin and an iodo porphyrin (either free base or zinc) are selectively joined via Pd(0)-catalyzed coupling reactions, affording a linear array with porphyrins in defined metalation states. Coupling of a zinc-porphyrin bearing iodo and ester groups with a free base porphyrin bearing ethyne and ester groups yielded the zinc-free base porphyrin dimer. Coupling of a bis-ethyne porphyrin with a porphyrin bearing iodo and ester groups afforded the porphyrin trimer. Cleavage of the esters yielded the amphipathic porphyrin dimer and trimer arrays. The arrays with adjacent zinc and free base porphyrins undergo efficient electronic energy transfer. Both amphipathic porphyrin arrays have been incorporated into L-alpha-phosphatidylcholine vesicles. This versatile synthetic strategy provides access to a family of porphyrin arrays for studies of photophysical processes in supramolecular assemblies.     

Singlet molecular oxygen quantum yield measurements of some porphyrins and metalloporphyrins

Hematoporphyrin IX dimethyl ester (HPDME), tetraphenylporphyrin (TPP), tetra(4-methoxyphenyl)porphyrin (TMPP), tetra(3,4-dimethoxyphenyl)porphyrin (TDMPP), tetra(3,4,5-trimethoxyphenyl)porphyrin (TTMPP), tetraanthrylporphyrin (TAP) and tetraacridylporphyrin (TACP), and their Zn²⁺, SnX ₂ ²⁺ , Pd²⁺ and Pt²⁺ complexes have been prepared and characterized. The singlet molecular oxygen quantum yield (ϕ_Δ) values of the above porphyrins and their metal derivatives in N,N-dimethyl formamide (DMF) have been measured in the presence of 1,3-diphenylisobenzofuran (DPBF) as¹O₂ acceptor using steady state technique after correcting for the intensity of light absorbed by the photosensitizers. The ϕ_Δ values for the free base porphyrins are usually around 0.60. Hematoporphyrin IX dimethyl ester and its metal derivatives follow the order: HPDME (ϕ_Δ = 0.60) > Zn HPDME (0.40) > PdHPDME (0.34) > Sn(OH)₂ HPDME (0.28) > PtHPDME (0.24). Zinc(II) complexes of tetraarylporphyrins show about 65% efficiency in ϕ_Δ values are compared to the ϕ_Δ values of their corresponding free base porphyrins. These results can be explained on the basis of catalyzed intersystem crossing to the ground state. The ϕ_λ values of the above free base porphyrins and their metal complexes in DMF in presence of DPBF using single-pulsed laser excitation technique follow similar trends.     

Modification of interfacial reactivity by the microenvironment. Metallation of porphyrins in monolayer films and assemblies

An investigation of metallation of several surfactant porphyrins in organized monolayer assemblies and at a monolayer film-solution interface is reported. The several surfactant porphyrins all readily incorporate Cu²⁺ in solution; in contrast metallation of the same compound with Cu²⁺ in assemblies and at a film-solution interface occurs at widely differing rates. The ease of metallation in the organized media can be correlated with the microenvironment of the porphyrin; porphyrins in hydrophilic sites in or near the interface are readily metallated while those in more hydrophobic sites are not. Several different metal ions can be incorporated into porphyrins lying near the hydrophilic interface; however, the order of reactivity differs appreciably from that observed in solution. Thus Mg²⁺, which is difficult to incorporate in solutions, is readily introduced, Co²⁺, Ni²⁺, Mn²⁺ and Zn²⁺ react well in both solution and assemblies while Ni²⁺ and Fe²⁺, which undergoes facile reaction in solution, are not incorporated into the assemblies.     

Solvent Dependency of Catalyst-Substrate Aggregation Through π-π Stacking in Photoredox Catalysis

Assemblies of photoredox catalysts and their target substrates prior to photoexcitation is a phenomenon naïvely overlooked by the majority of synthetic chemists, but can have profound influences on reactivity and selectivity in photocatalytic reactions. In this study, we determine the aggregation states of triarylamine radical cationic photocatalysts with various target arene substrates in different solvents by specifically parameterized polarizable molecular dynamics simulations. A π-stacking interaction previously implicated by more expensive, less-representative quantum calculations is confirmed. Critically, this study presents new insights on: i) the ability of solvents (MeCN vs DMF) to make or break a photocatalytic reaction by promoting (MeCN) or demoting (DMF) its catalyst-substrate assemblies, which is a determining factor for reactivity, ii) the average “lifetimes” of assemblies in solution from a dynamic simulation. We find that both in the ground state and the photoexcited state, the cationic radical assemblies remain intact for periods often higher than 60 ps, rendering them ideally suitable to undergo intra-assembly electron transfer reactions upon photoexcitation. Such aspects have not addressed by previous studies on synthetic photocatalytic reactions involving non-covalent assemblies.     

Synthesis, electrochemical, and photophysical studies of multicomponent systems based on porphyrin and ruthenium(II) polypyridine complexes

Two ruthenium tris-bipyridine functionalized porphyrins 4, 8 and their Zn derivatives 4-Zn, 8-Zn were designed, synthesized, and characterized. The redox potentials of these complexes as well as their corresponding monomeric reference porphyrin and ruthenium bipyridine complexes were also measured for comparison. Primary dynamic studies on the electron injection and backing recombination between these complexes and TiO₂ nanoparticles were carried out by means of transient absorption spectroscopy. The results indicate that a long-lived charge separation state was obtained in these assemblies.     

Mapping the Electronic Structure and the Reactivity Trends for Stabilized α-Boryl Carbanions

The chemistry of stabilized α-boryl carbanions shows remarkable diversity, and can enable many different synthetic routes towards efficient C−C bond formation. The electron-deficient, trivalent boron center stabilizes the carbanion facilitating its generation and tuning its reactivity. Here, the electronic structure and the reactivity trends of a large dataset of α-boryl carbanions are described. DFT-derived parameters were used to capture their electronic and steric properties, computational reactivity towards model substrates, and crystallographic analysis within the Cambridge Structural Dataset. This study maps the reactivity space by systematically varying the nature of the boryl moiety, the substituents of the carbanionic center, the number of α-boryl motifs, and the metal counterion. In general, the free carbanionic intermediates are described as borata-alkene species with C−B π interactions polarized towards the carbon. Furthermore, it was possible to classify the α-boryl alkylidene metal precursors into three classes directly related to their reactivity: 1) nucleophilic borata-alkene salts with alkali and alkaline earth metals, 2) nucleophilic η²-(C−B) borata-alkene complexes with early transition metals, Cu and Ag, and 3) α-boryl alkyl complexes with late transition metals. This trend map aids selection of the appropriate reactive synthon depending on the reactivity sought.     

Porphyrin Containing Polymersomes with Enhanced ROS Generation Efficiency: In Vitro Evaluation

Porphyrins are molecules possessing unique photophysical properties making them suitable for application in photodynamic therapy. The incorporation of porphyrins into natural or synthetic nano‐assemblies such as polymersomes is a strategy to improve and prolong their therapeutic capacities and to overcome their limitations as therapeutic and diagnostic agents. Here, 5,10,15,20‐tetrakis(1‐(6‐ethoxy‐6‐oxohexyl)‐4‐pyridin‐1‐io)‐21H,23H‐porphyrin tetrabromide porphyrin is inserted into polymersomes in order to demonstrate that the encapsulation enhances its ability to generate highly reactive singlet oxygen (¹O₂) upon irradiation in vitro. The photoactivation of the free and polymersome‐encapsulated porphyrin is evaluated by electron spin resonance and cell viability assays on three different mammalian cell lines. The results indicate that by encapsulating the porphyrin, a controlled ROS delivery within the cells is achieved, at the same time avoiding side effects such as dark toxicity, non‐specific porphyrin release and over time decreased activity in vitro. This work focuses on showing a not‐toxic model system for modern therapeutic nanomedicine, which works under mild irradiation and dosage conditions.     

Spectroscopic Investigations of Porphyrin-TiO2 Nanoparticles Complexes

This study presents the spectral characterization of TiO₂ nanoparticles (NPs) functionalized with three porphyrin derivatives: 5,10,15,20-(Tetra-4-aminophenyl) porphyrin (TAPP), 5,10,15,20-(Tetra-4-methoxyphenyl) porphyrin (TMPP), and 5,10,15,20-(Tetra-4-carboxyphenyl) porphyrin (TCPP). UV-Vis absorption and Fourier transform infrared spectroscopy–attenuated total reflection (FTIR-ATR) spectroscopic studies of these porphyrins and their complexes with TiO₂ NPs were performed. In addition, the efficiency of singlet oxygen generation, the key species in photodynamic therapy, was investigated. UV-Vis absorption spectra of the NPs complexes showed the characteristic bands of porphyrins. These allowed us to determine the loaded porphyrins on TiO₂ NPs functionalized with porphyrins. FTIR-ATR revealed the formation of porphyrin-TiO₂ complexes, suggesting that porphyrin adsorption on TiO₂ may involve the pyrroles in the porphyrin ring, or the radicals of the porphyrin derivative. The quantum yield for singlet oxygen generation by the studied porphyrin complexes with TiO₂ was higher compared to bare porphyrins for TAPP and TMPP, while for the TCPP-TiO₂ NPs complex, a decrease was observed, but still maintained a good efficiency. The TiO₂ NPs conjugates can be promising candidates to be tested in photodynamic therapy in vitro assays.     

Complex Formation and Spectral Properties of meso-Phenyltetrabenzoporphyrins in Pyridine and N,N-Dimethylformamide

Contributions of structural (macroring distortion) and polarization (in asymmetrically substituted derivatives) effects into the reactivity and chromophoric properties of substituted porphyrins were revealed on the basis of the kinetics of complex formation of nona-, deca-, undeca-, and dodecasubstituted porphyrins (meso-phenyltetrabenzoporphyrins) with Zn(OAc)₂ in pyridine and the electronic absorption spectra of the ligands and their complexes with Zn(II) and Cu(II) in pyridine and N,N-dimethylformamide (DMF). Dodecaphenyl substitution produces a weaker ring distortion in the more aromatic tetrabenzoporphyrin compared with porphyrins themselves. Irrespective of the degree of macroring nonplanarity, the Zn (II) and Cu complexes of tetrabenzoporphyrins with increasing degree of meso-phenyl substitution meet a spectral stability criterion.     

Stand up for Electrostatics: The Disiloxane Case

The basicity of the simplest silicone, disiloxane (H₃Si−O−SiH₃), is strongly affected by the Si−O−Si angle (α). We use high-level ab initio MP2/aug′-cc-pVTZ calculations and the molecular electrostatic potential (MEP) to analyze the relationship between the increase in basicity and the reduction of α. Our results clearly point out that this increase can be explained through the MEP, as the interactions between oxygen from disiloxane and the acceptors are mostly electrostatic. Furthermore, the effect of α on the tetrel bond between disiloxane and several Lewis bases can again be rationalized using the MEP. Finally, we explore the cooperativity throughout α for ternary complexes where disiloxane simultaneously interacts with a Lewis acid and a Lewis base. Both non-covalent interactions remain cooperative for all α values, although the largest cooperativity effects are not always those maximizing the binding energy in the binary complexes. Overall, the MEP remains a powerful predictor for noncovalent interactions.     

Synthesis, characterization, and reactivities of manganese(V)-oxo porphyrin complexes

The reactions of manganese(III) porphyrin complexes with terminal oxidants, such as m-chloroperbenzoic acid, iodosylarenes, and H(2)O(2), produced high-valent manganese(V)-oxo porphyrins in the presence of base in organic solvents at room temperature. The manganese(V)-oxo porphyrins have been characterized with various spectroscopic techniques, including UV-vis, EPR, 1H and 19F NMR, resonance Raman, and X-ray absorption spectroscopy. The combined spectroscopic results indicate that the manganese(V)-oxo porphyrins are diamagnetic low-spin (S = 0) species with a longer, weaker Mn-O bond than in previously reported Mn(V)-oxo complexes of non-porphyrin ligands. This is indicative of double-bond character between the manganese(V) ion and the oxygen atom and may be attributed to the presence of a trans axial ligand. The [(Porp)Mn(V)=O](+) species are stable in the presence of base at room temperature. The stability of the intermediates is dependent on base concentration. In the absence of base, (Porp)Mn(IV)=O is generated instead of the [(Porp)Mn(V)=O](+) species. The stability of the [(Porp)Mn(V)=O](+) species also depends on the electronic nature of the porphyrin ligands: [(Porp)Mn(V)=O](+) complexes bearing electron-deficient porphyrin ligands are more stable than those bearing electron-rich porphyrins. Reactivity studies of manganese(V)-oxo porphyrins revealed that the intermediates are capable of oxygenating PPh(3) and thioanisoles, but not olefins and alkanes at room temperature. These results indicate that the oxidizing power of [(Porp)Mn(V)=O](+) is low in the presence of base. However, when the [(Porp)Mn(V)=O](+) complexes were associated with iodosylbenzene in the presence of olefins and alkanes, high yields of oxygenated products were obtained in the catalytic olefin epoxidation and alkane hydroxylation reactions. Mechanistic aspects, such as oxygen exchange between [(Porp)Mn(V)=16O](+) and H(2)(18)O, are also discussed.     

Porphyrin complexes of the period 6 main group and late transition metals

Metalloporphyrin complexes of the period six metals gold, mercury, thallium, lead and bismuth are often overlooked in favour of their lighter congeners. These complexes exhibit unusual coordination geometries, prominently featuring the metal centre residing out the porphyrin plane. Not only are these compounds chemically interesting, but several applications for these complexes are beginning to emerge. Gold and bismuth porphyrins have medicinal applications including novel chemotherapeutics and sensitizers for α-radiotherapy, while gold porphyrins have applications in materials chemistry and catalysis. This perspective serves to highlight trends in the synthesis and structure of these heavy metal complexes as well as illustrate the considerations necessary for rationally designing elaborate porphyrin architectures.     

Synthesis and Characterization of a Series of Cationic Porphyrins Having Different Steric Effects

Abstract

A series of cationic porphyrins having only different steric effects and their cobalt complexes were synthesized. The cations of these porphyrins are meso-tetrakis(4-N-propylpyridyl)porphyrin (TPPyP⁴⁺), meso-tetrakis(4-N-ethylpyridyl)porphyrin (TEPyP⁴⁺) and meso-tetrakis(4-N-methylpyridyl)porphyrin (TMPyP⁴⁺), respectively. The anions are I^? (water soluble porphyrins) and ClO₄ ^? (organic solvent soluble porphyrins), respectively. The synthetic cationic porphyrins were characterized by elemental analysis, UV-visible absorption spectra, FTIR, MALDI-TOF-MS and ¹H-NMR spectra.     

Synthesis, characterization, and preliminary intramolecular energy transfer studies of rigid, emissive, rhenium-linked porphyrin dimers

The reaction of pyridyl functionalized porphyrins with Re(CO)(5)Cl in THF results in the formation of porphyrin dimers which, despite incorporation of rhenium into the assemblies, remain fluorescent. The rigid compounds provide an efficient geometry and/or orbital pathway for singlet energy transfer, rendering these compounds suitable, in principle, for the study of both through-bond and through-space energy transfer. Derivatives containing both metallated and freebase porphyrins connected via the metal corners display efficient porphyrin-porphyrin energy transfer. The photophysical properties of the assemblies have been studied by both steady-state and time-resolved fluorescence techniques, yielding approximate rates and efficiencies for porphyrin-porphyrin energy transfer.     

Porphyrin derivatives: Synthesis and potential applications

Porphyrin‐porphyrin and porphyrin‐chlorin dimers have been synthesized and evaluated for their photo‐physical and in vivo photodynamic therapy properties. Two of them can become potential new photosensitizers. Study of the reactivity of meso‐tetraaryl porphyrins, as dienophiles, in Diels‐Alder transformations and as dipolarophiles in 1,3‐dipolar cycloadditions, has been undertaken. New synthetic methodologies for certain chlorin, bacteriochlorin and isobacteriochlorin type macrocycles, with potential biological significance, have been established.     

5-Substituted dipyrranes: synthesis and reactivity

Dipyrranes constitute important building blocks in the synthesis of porphyrins, corroles, chlorins, calix[4]pyrroles, porphodimethenes, BODIPY dyes and dipyrrinato complexes. This tutorial review describes the overall progress made in the last twenty years in this field, mainly focusing on the most practical and useful synthetic methodologies and offers a critical comparison of various conditions reported in the literature. This review also deals with the reactivity of 5-substituted dipyrranes presenting the scope of their reactions with electrophiles.     

Sequential energy and electron transfer in aggregates of tetrakis[oligo(p-phenylene vinylene)] porphyrins and C60 in water

Chiral aggregation of oligo(p-phenylene vinylene)-functionalized Zn and free-base porphyrins is observed in water. The formation of mixed assemblies containing both porphyrins results in sequential energy transfer from OPV via zinc porphyrin to free-base porphyrin. Furthermore, the incorporation of C60 as electron acceptor yields a charge separated state by ultimate electron transfer.     

Reactivity of N-substituted azaaromatics

In the present review dealing with the reactivity of N-substituted azaaromatics their reduction as well as reactions proceeding on ring carbon atoms and on nitrogen atoms are described; also the reactivity of porphyrins and of complexes possessing these systems is reported.