Journal of Porphyrins and Phthalocyanines

Some of the most important achievements of Tomás Torres in the last few decades within the fields of Phthalocyanines and related compounds, Molecular Materials and Nanoscience are revised and his recognized international prestige in these areas highlighted on the occasion of his 65th birthday.

Preparation of porphyrins which do not aggregate, possessing low melting points is an endearing challenge for several applications in materials science. In this contribution a viewpoint regarding the synthesis of low melting point porphyrins, is presented. Herein we review the synthesis of symmetrical and unsymmetrical substituted porphyrins that hold the possibility to be used in several materials science applications and present new results on the spectroscopic and thermal characterization of some low melting point meso-tetrasubstituted porphyrins.

In 1960, MacDonald and coworkers introduced a new method for porphyrin synthesis that involved the acid-catalyzed condensation of dipyrrylmethane dialdehydes with $\alpha$,${\alpha }^{\prime }$-diunsubstituted dipyrrylmethanes or the related dicarboxylic acids, followed by an air oxidation. The key bond forming steps entail electrophilic substitution at two pyrrole units with the aldehyde moieties to generate, following elimination of water, a 5,15-dihydroporphyrin or porphodimethene intermediate. Following addition of sodium acetate, or in later procedures zinc acetate, the dihydroporphyrins readily air oxidize to the fully aromatic porphyrin system. This strategy, which parallels chemistry contemporaneously developed by R. B. Woodward at Harvard for the total synthesis of chlorophyll $a$, demonstrated that dipyrrylmethanes were sufficiently stable to be utilized as intermediates in porphyrin syntheses and that porphodimethene formation circumvented acidolytic scrambling reactions that might lead to isomeric porphyrin products. This type of chemistry was later adapted by Johnson, Woodward and others to prepare porphyrin-type systems by a “3 + 1” strategy, or expanded porphyrins by “3 + 2” or other combinations of oligopyrrolic precursors. In recent years, the term “MacDonald condensation” has been increasingly used to describe other types of chemistry involving oligopyrrolic intermediates. Following on from a historical review of this area, guidelines for the identification of MacDonald-type reactions are proposed.

Arrays of phthalocyanine-based sensors with complementary activity have been used to develop voltammetric electronic tongues. Such systems have demonstrated to be useful in enology for the evaluation of quality of wines in different production stages, from grapes to bottles. In this paper, the state of the art of multisensor systems based on phthalocyanines dedicated to the analysis of musts (juices obtained from crushed grapes) is described. Such multisensor systems cover different types of sensors from simple Carbon Paste Electrodes, to sophiticated nanostructured sensors, including Langmuir–Blodgett or Layer by Layer thin films and biomimetic biosensors where phthalocyanines play a crucial role as electron mediator between enzymes and electrodes. In all cases, multisensor systems based on phthalocyanines have been able to discriminate musts prepared from different varieties of grapes. The performance of these systems can be improved by combining non-specific sensors with biosensors containing enzymes selective to phenols. In this case, excellent relationships have been found between the responses provided by the array and the content in phenols and acids provided by traditional chemical analysis.

Phosphorus complexes of porphyrinoids such as porphyrins, corroles, $N$-fused porphyrins, $N$-fused expanded porphyrins and expanded porphyrins can be prepared readily by treating the porphyrinoid with phosphorylating agents such as PX₃, PX₅ and POX₃ (X $=$ Cl or Br) under standard reaction conditions. In phosphorus porphyrinoids, the phosphorus is generally high valent $+$5 oxidation state and the coordination number is varied from four to six. The insertion of P(V) into porphyrinoids alters the structure and electronic properties of the macrocycle significantly. Specially, the phosphorus binding mode is different from one porphyrinoid to another. The oxophilicity nature of P(V) in P(V) porphyrinoids is very useful to change variety of axial ligands and also helps to synthesize multi-porphyrin arrays by axial bonding approach. This review summarizes the phosphorus complexes of five different porphyrinoids and discusses their structure and electronic properties as well as their applications in the synthesis of more elaborate P(V) porphyrinoid based architectures.

Click chemistry has become a very popular and efficient concept for synthetic chemists for the construction of new molecules. Among the click chemistry approaches known to date, it is undoubted that the copper-catalyzed alkyne-azide 1,3-dipolar cycloaddition (CuAAC) has played a key role. Such reactions in general offer virtually unlimited possibilities to prepare new molecules for $e.g$. materials science applications. As such, the synthesis of porphyrin–fullerene conjugates obtained via CuAAC are summarized within the present review article.

The conversion of solar energy into chemical energy by the reduction of small molecules provides a promising solution for the effective energy storage and transport. In this manuscript, we have highlighted our recent researches on the catalysis of cobalt-macrocycle complexes for the reduction of O₂, proton and CO₂. We have successfully clarified the reaction mechanisms of catalytic O₂ reduction with cobalt phthalocyanine (Co${}^{II}$(Pc)) and cobalt chlorin (Co${}^{II}$(Ch)) based on detailed kinetic study under homogeneous conditions. The presence of proton-accepting moieties on these macrocyclic ligands enhances the electron-accepting ability, leading to the efficient catalytic two-electron reduction of O₂ to produce hydrogen peroxide (H₂O${}_2)$ with high stability and less overpotential in acidic solutions. When Co${}^{II}$(Ch) is adsorbed on multi-walled carbon nanotubes (MWCNTs) and employed as an electrocatalyst, CO₂ was successfully reduced to form CO with a Faradaic efficiency of 89% at an applied potential of -1.1 V vs. NHE in an aqueous solution. Finally, photocatalytic H₂ evolution was attained from ascorbic acid with Co${}^{II}$(Ch) as a catalyst and [Ru(bpy)₃]${}^{2+}$ (bpy $=$ 2,2$\prime$-bipyridine) as a photocatalyst via a one-photon two-electron process.

Over the last two decades the preparation of pyrrole-based receptors for anion recognition has attracted considerable attention. In this regard porphyrins, phthalocyanines and expanded porphyrins have been used as strong and selective receptors while the combination of those with different techniques and materials can boost their applicability in different applications as chemosensors and extracting systems. Improvements in the field, including the synthesis of this kind of compounds, can contribute to the development of efficient, cheap, and easy-to-prepare anion receptors. Extensive efforts have been made to improve the affinity and selectivity of these compounds and the continuous expansion of related research makes this chemistry even more promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles.

This review, dedicated to Professor Tomás Torres on the occasion of his 65th birthday, offers an overview of the main achievements in his research career. Having a strong background in organic chemistry, he and his group have constantly devoted much effort to the development of synthetic methods towards novel systems based on phthalocyanines and other porphyrinoid analogues. Not less important, the founding of solid collaborations with other prominent scientists has led to study the physicochemical properties of these $\pi$-conjugated dyes, and to evaluate their potential application in multidisciplinary areas such as self-assembly, nanochemistry, optoelectronics and biomedicine.

A subphthalocyanine-fullerene dyad, 1 was newly synthesized through axial functionalization via central boron of subphthalocyanine with $p$-hydroxybenzaldehyde, and subsequent dipolar cycloaddition reaction of fullerene. The subphthalocyanine entity was peripherally functionalized with moderately electron rich 4-iodophenoxy substituents to probe their effect on photoinduced processes within the SubPc-C${}_{60}$ dyad. Optical absorbance studies revealed presence of both entities of the dyad while steady-state fluorescence studies revealed quenching of subphthalocyanine emission in the dyad in both nonpolar toluene and polar benzonitrile solvents. Further, redox potentials of the donor and acceptor entities were obtained by differential pulse voltammetry, and energy of different photochemical processes was evaluated. Femtosecond transient absorption studies revealed occurrence of charge separation in the SubPc-C${}_{60}$ dyad either from the ¹SubPc* or ¹C${}_{60}$* in both nonpolar and polar solvents. That is, transient peaks in the 665 nm range corresponding to SubPc${}^{•+}$ and at 1015 nm corresponding to C${}_{60}^{•-}$ was possible to spectrally identify. The measured rate of charge separation, $k_{CS}$ was found to be ∼7.0 × 10${}^{10}$ s${}^{-1}$ irrespective of the solvent. The rate of charge recombination, $k_{CR}$ from the decay of the C${}_{60}^{•-}$ peak was found to be 1.1 × 10⁹ s${}^{-1}$ in toluene and 1.3 × 10⁹ s${}^{-1}$ in benzonitrile, respectively. The SubPc${}^{•+}$-C${}_{60}^{•-}$ radical ion-pair populated the low-laying ³SubPc* prior returning to the ground state.

Triphenylphosphine was added regioselectively at the C(3) position of bis-Au(III) complex of [26]hexaphyrin 5 in the presence of trifluoroacetic acid to produce [28]hexaphyrin triphenylphosphine adduct 6 in 62% yield, which has been fully characterized by NMR, UV-vis/NIR absorption, and MS spectroscopies, and X-ray diffraction analysis. The rigid planar structure forces 6 to take Hückel antiaromaticity, which has been supported by its ¹H NMR spectrum. Curiously, the detailed structural analysis elucidated that the triphenylphosphine moiety exists as a phosphorane form in the solid state. A plausible mechanism via a double protonated 5 is proposed, which can explain the observed regioselectivity.

Three zwitterionic meso-substituted A₃B- and AB₂C-porphyrins containing one sulfonato alkylpyridinium substituent and three or two alkoxy-substituted phenyl groups were synthesized in good yield and fully characterized as to their physicochemical properties by a variety of techniques. This new series of inner salt donor-acceptor meso-substituted porphyrin derivatives were prepared for possible application as amphiphilic probes for membrane insertion in the area of combined second-harmonic and two-photon fluorescence cellular microscopy. To this end, the linear and nonlinear optical properties of the compounds were characterized, together with their electrochemical and spectroelectrochemical properties in non-aqueous media. The neutral design of such molecules enabled us to determine their second order non-linear properties, both by Electric Field Induced Second Harmonic Generation and Hyper–Rayleigh Scattering. Two-photon absorption cross sections of these dyes were also measured by the two-photon induced fluorescence method. The zwitterionic nature of the inner salt results in very specific solvent-dependent redox-properties, which could be rationalized in terms of solvent-dependent ion-pairing. The overall data electrochemical and photophysical data indicates that these new porphyrinic systems should be good probes for membrane potential sensing.

A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.

Two bis-tetraphenylporphyrin tweezers-like conjugates bearing different linkers have been characterized by means of electrochemical and photophysical methods. The thrust of this work was the complexation of these bis-porphyrins with C${}_{60}$ and metallic nitride endohedral fullerenes (MNEF) like Sc₃N@C${}_{80}$ in organic and in aqueus media — studied by a combination of steady-state and time-resolved spectroscopies. In the context of charge separation evidence for the formation of the 1a${}^{(•+)}$-Sc₃N@C${}_{80}^{(•-)}$ and 1c${}^{(•+)}$-Sc₃N@C${}_{80}^{(•-)}$ charge separated states in organic and aqueous media, respectively, came from transient absorption spectroscopy. Multi-wavelength analyses afforded charge separated state lifetimes of around 400 ps.

A novel subphthalocyanine containing bulky substituents placed at its peripheral sites (i.e. 2,3,9,10,16,17-hexa(2′,6′-di-iso-propylphenoxy)boron subphthalocyanine) was prepared and assessed for supramolecular binding with C${}_{60}$, through crystallisation and fluorescence studies. Three different crystal polymorphs of the subphthalocyanine were obtained that showed inclusion of a single aromatic solvent molecule within the well-defined cavity of the molecule but complete exclusion of C${}_{60}$. Analysis of the crystal structures indicated that the bowl-shaped cavity of the subphthalocyanine molecule was only accessible to small molecules due to the steric congestion surrounding the macrocycle, which results in hindered rotation of the substituents on the NMR timescale. Enhanced solubility, up to 42.0 g/L in common organic solvents, was demonstrated consistent with the crystal structures which are dominated by relatively weak intermolecular interactions, which allow solvent molecules to play a role in crystallisation.

Water-soluble derivatives of three kinds of expanded porphyrins (N-fused pentaphyrin, hexaphyrin, and heptaphyrin) were synthesized and their binding ability to G-quadruplex (G4-) DNA was evaluated. The inhibitory effects on enzymatic telomere extension were also investigated together with other tetrapyrrolic porphyrinoids. While expanded porphyrins increased the melting temperature of G4-DNA more effectively than the regular porphyrins, a porphyrin isomer (N-confused porphyrin) showed the highest inhibitory effect on telomerase activity.

A novel isoindole-containing polyaromatic hydrocarbon was unexpectedly formed during the synthesis of meso-2,6-dichlorophenyl-substituted tribenzosubporphyrin from a reaction of phthalimide and 2,6-dichlorophenylacetic acid in the presence of boric acid. Due to the highly annulated structure, this molecule exhibited blue color in solution, which was theoretically well reproduced by the HOMO–LUMO transitions based on the time-dependent DFT calculation. In this manuscript, the synthesis and properties of this polyaromatic hydrocarbon and meso-2,6-dichlorophenyl-substituted tribenzosubporphyrin are reported.

A concise and versatile strategy for the preparation of isoamethyrins is presented. The novel procedure is predicated on the acid catalyzed condensation of a quaterpyrrole and a bipyrrole dialdehyde. As application of this procedure an aryl substituted isoamethyrin has been synthetized and characterized.

Liquid-crystalline gold nanoparticles were prepared by grafting mesomorphic $\alpha$,$\beta$-unsaturated carbonyl olefins onto the organic shell of gold nanoparticles containing terminal olefin ligands by applying the olefin cross-metathesis. The latter reaction was performed under standard conditions using second-generation Grubbs catalyst. The title materials were found to be stable up to 200$deg$ C and gave rise to the formation of smectic A phases in agreement with the structure and nature of the liquid-crystalline promoters. The olefin cross-metathesis proved to be a reaction of choice for the design of liquid-crystalline nanoparticles.

We report the synthesis, characterization and electrical properties of lanthanide metal based bis-phthalocyanines, {M[Pc-(β-HHT)₄]₂} (HHT:1-hydroxyhexane-3-ylthio){ M $=$ Lu${}^{3+}$ (2), Eu${}^{3+}$ (3), and Yb${}^{3+}$ (4)}. The interaction of bis-phthalocyanines with Ag${}^{+}$ and Pd${}^{2+}$ metal ions were investigated by UV-vis spectroscopy and atomic force microscopy. Thin films of bis-phthalocyanine molecules were prepared by spin-coating method. The surface morphology of thin films were performed with Atomic Force Microscopy as further investigate. The electrical transport properties of ITO/Pc/Al devices were investigated. At low voltages all the films showed an ohmic conduction, whereas at higher voltage levels the conduction is dominated by space charged limited conduction with exponential distribution of trapping levels. Measurements of current density as a function of inverse temperature at constant applied voltage yielded a hole mobility values, μ_p${}_{}=2.12\times 10^{-7}$, $6.72\times 10^{-7}$ and $1.58\times 10^{-6}$ m².sn${}^{-1}$.V${}^{-1}$ for lanthanium phthalocyanines. From the analysis of frequency, ω, dependence of electrical conductivity, σ_ac. it was found that the ${\sigma }_{ac}$ obeys the power law given by σ_ac = Aω^s, in which the frequency exponent “s” decreases with temperature.

Octa-(meta-methoxyphenyl) substituted tetraazaporphyrin (TAP, 1) and corrolazine (Cor, 4) phosphorus(V) complexes have been synthesized and characterized. 1 has a blue-shifted, small charge transfer (CT) band while para-methoxyphenyl substituted PTAP 2 has a red-shifted, intense CT band. The difference could be interpreted as an inductive effect of the meta-methoxy groups. The position and intensity of the absorption bands of 1 are well matched to the trend of para-substituted PTAPs. The synthesis of PCor from free-base TAP was also investigated. The PCor was not generated directly but from a PTAP intermediate

A subphthalocyanine-dithienylethene dyad has been synthesized and characterized by ¹H-, ${}^{13}$C-NMR, HR-MS, UV-visible and emission spectroscopy. The results show that photoinduced isomerization of dithienylethene moiety from close-form to opened form can be achieved under visible light using subphthalocyanine as a light-harvesting unit and the fluorescence properties of subphthalocyanine could be modulated by the isomerization state of the dithienylethene moiety.

A new low-symmetry tetraazaporphyrin has been synthesized and characterized by ¹H NMR, electronic spectroscopies and high resolution mass spectrometry. The photophysical behavior of the newly synthesized low-symmetry zinc tetraazaporphyrin ZnPz 1 has been examined and compared with that of the symmetrical tert-octylphenoxy zinc phthalocyanine ZnPc 2, by using steady-state absorption and fluorescence, cyclic voltammetry, molecular orbital calculation, and femtosecond transient absorption techniques.

A reaction between 5,10,15,20-tetra(4-hydroxyphenyl)porphyrin and 1-bromopyrene resulted in the formation of 5,10,15,20-tetra[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (1), while cross-condensation between 4-(4-(pyrenyl-1)butoxy)benzaldehyde, ferrocenecaboxaldehyde, and pyrrole resulted in the formation of 5-ferrocenyl-10,15,20-tri[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (2), 5,10-diferrocenyl-15,20-di[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (3), and 5,15-diferrocenyl-10,20-di[4-(4-(pyrenyl-1)butoxy)phenyl]porphyrin (4). All pyrene-containing porphyrins were characterized by ¹H NMR, UV-vis, MCD, and high-resolution ESI methods, while their electronic structures and the nature of the excited states were elucidated using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The molecular structure of 1 and its fluorescence quenching upon the addition of C${}_{60}$ fullerene was also investigated using X-ray crystallography and steady-state fluorescence approaches.

A series of symmetrically substituted subphthalocyanine derivatives with diverse substituent such as electron-donating or electron-withdrawing moieties at the peripheral position have been synthesized and their photophysical and electrochemical properties have been investigated. Solution-processed bulk heterojunction (BHJ) organic solar cells using SubPc derivatives as electron donor and fullerene derivative PCBM as an electron acceptor in the active layer were fabricated and characterized to evaluate the photovoltaic behavior of these molecules.

The basicity of azomethine nitrogens was studied on a series of phthalocyanines (Pcs) that differed in a position of substituent, $i.e.$ peripherally ($\beta$-series) and non-peripherally substituted Pcs ($\alpha$-series), and in a type of substituent (alkylsulfanyl, alkyloxy or alkyl). Appropriate 3,6- or 4,5-disubstituted phthalonitriles were prepared either by nucleophilic substitution or by Negishi coupling. Target zinc Pcs were synthesized by Linstead method. The basicity was studied by the mean of absorption and ¹H NMR spectroscopies in chloroform upon titration with trifluoroacetic acid. Equilibrium constants (log $K$) indicated significant difference within the series. Basicity decreased as follows: $\alpha$-alkyloxy ≫ $\alpha$-alkylsulfanyl > $\beta$-alkyloxy > $\beta$-alkyl > $\beta$-alkylsulfanyl ∼ $\alpha$-alkyl with log $K$ higher than 7 down to 2.6 M${}^{-1}$. Increased basicity of $\alpha$-alkyloxy and $\alpha$-alkylsulfanyl Pcs is caused by the stabilization of trapped hydrogen at azomethine nitrogen via hydrogen bonding and van der Waals interactions, respectively. The basicity of $\beta$-series clearly correlated with the electronic effects of substituents. ¹H NMR studies confirmed the possibility of the weak bonding interactions in $\alpha$-alkyloxy and $\alpha$-alkylsulfanyl Pcs, however, the position of the ¹H NMR signal of azomethine-NH proton was even more influenced by the electronic effects of present substituents than by the weak interactions.

Phenoxy-substituted boron subphthalocyanine, blended with a conductive polymer MEH-PPV, is presented as a photoresistive organic material. Using an easily accessible drop casting technique, the blend produces a thin-layer organic photoresistor with a photoresistive ratio of ~2–12. Variations in the blend composition and morphology are shown to change the transport properties of the material. The photoelectrochemical characteristics of the photoresistor are discussed in terms of impedance spectroscopy and the morphology of the material is analyzed using confocal fluorescent microscopy. The device developed is a daylight detector.

In this work, we report on the synthesis and characterization of two fulleropyrrolidines bearing porphyrin/phthalocyanine and bis-phthalocyanine tweezers. The self-assembly properties in different solvents have been investigated by AFM and SEM. When deposited on surface from dichloromethane solutions, the fullerene derivatives formed aggregates of ca. 4–8 nm in height while hollow nanospheres with diameters of ca. 300–1000 nm are obtained from crystallization attempts.

Ferrocene-subphthalocyanine dyads characterized, where ferrocene is axially linked with subphthalocyanine at its axial position with the B–O bond through the para and metapositions, namely Fc–$p$PhO–SubPc (dyad 1) and Fc–$m$PhO–SubPc (dyad 2). The geometric and electronic structures of 1 and 2 were probed by ab initio B3LYP/6-311G methods. The optimized structures showed that the Fc and SubPc entities are separated by 8.42 and 7.40 Å for dyads 1 and2, respectively. The distribution of the highest occupied frontier molecular orbital (HOMO) was found to be located on the Fc entity, while the lowest unoccupied molecular orbital (LUMO) was located on the SubPc entity, suggesting that the charge-separated states of the are Fc${}^{+}$–SubPc${}^{•-}$. Upon photoexcitation at the subphthalocyanine unit, both dyads undergo photoinduced electron transfer to form the corresponding charge-separated species, Fc${}^{+}$–SubPc${}^{•-}$. Based on their redox potentials determined by cyclic voltammetry technique, the direction of the charge separation and the energies of these states have been revealed. Femtosecond transient spectroscopic studies have revealed that a fast charge separation of 8.8 × 10${}^{10}$ and 1.2 × 10${}^{11}$ s${}^{-1}$ for 1 and 2, respectively, indicating fast charge separation in these simple dyads.

This work describes the synthesis of ruthenium(IV) $\mu$-oxo porphyrin complexes of general formula [Ru^IV(TPP)(X)]₂O which have been applied as catalysts in nitrene transfer reactions using aryl azides (ArN${}_3)$ as nitrene sources. Collected data indicated that the catalytic efficiency of [Ru^IV(TPP)(OCH${}_3)$]₂O was comparable to that of Ru^II(TPP)CO because of their analogous reactivity towards aryl azides to give the same catalytically active bis-imido species Ru^VI(TPP)(ArN)₂. The reaction of [Ru^IV(TPP)(OCH${}_3)$]₂O with Ph₃CN₃ or (CH${}_3{)}_3$SiN₃ afforded [Ru^IV(TPP)(N${}_3)$]₂O which was fully characterised, its molecular structure was also determined by single crystal X-ray analysis.

Polymeric copper and cobalt phthalocyanine (Cu-pPc and Co-pPc) were prepared as thin films on fluorine-doped tin oxide (FTO) glass from evaporated metal films via a chemical vapor deposition (CVD) process with 1,2,4,5-tetracyanobenzene (TCB). The films were characterized by optical absorption spectroscopy in transmission and by X-ray photoelectron spectroscopy. Different oxidation states of the metal atoms were detected indicating different chemical environments. Reversible electrochemical reduction of Cu-pPc and Co-pPc was observed and monitored by cyclic voltammetry and spectroelectrochemical investigations. Cyclic voltammetry and chronoamperometry in the positive voltage range led to anodic currents in the oxygen evolution reaction that could be performed at stable current densities and showed a remarkable efficiency in particular for electrodes of Co-pPc in this reaction, attractive for the conversion of electrical energy into chemical energy.

Zinc phthalocyanine possessing triphenylamine at its peripheral position has been synthesized and its optical, emission, electrochemical and third-order nonlinear optical (NLO) properties were investigated. Soret band was broadened due to the presence of triphenylamine moiety. Electrochemical properties indicated that both oxidation and reduction processes were ring centered. Emission spectra were recorded in different solvents and the fluorescence yields obtained were in the range of 0.02–0.17 while the time-resolved fluorescence data revealed radiative lifetimes of typically few ns. Third-order NLO properties of this molecule have been examined using the Z-scan technique with picosecond (ps) and femtoseocnd (fs) pulses. Closed and open aperture Z-scan data were recorded with 2 ps/1 50 fs laser pulses at a wavelength of 800 nm and NLO coefficients were extracted from both the data. Our data clearly suggests the potential of this molecule for photonics applications.

An organosoluble phthalocyanine substituted by four silylated tetraethyleneglycol chains was designed. This phthalocyanine become water-soluble after acid-promoted removal of the TBDMS moieties (which does not occur in acetonitrile), and is therefore a naked-eye observation system of acid aqueous media. Fluoride anion sensitivity based on the same principle proved unfortunately unsuccessful.

Photo-excitation under visible light has been an important step to acquire solar-driven TiO₂ photocatalysts and dye sensitization has been used frequently to extend the optical response of TiO₂ into the visible region. In the present work, new heterogeneous photocatalysts were prepared by anchoring carboxylic acid substituted Zn(II) and Co(II) phthalocyanines onto polycrystalline TiO₂ surface and their photocatalytic activities were investigated. Due to covalent bonding of carboxy-terminated molecules onto TiO${}_2$semiconductors, we synthesized symmetric 4-hydroxybenzoic acid-bearing metallophthalocyanines as dye sensitizer molecules. Heterogeneous composites having titanium dioxide and metallophthalocyanines anchored via CO–O–TiO₂ bonds were characterized by using X-ray diffraction (XRD), Fourier-transform infrared spectrometry (FT-IR), and ultraviolet-visible diffuse reflectance spectroscopy. The optimum loading value of the dyes on TiO₂ were 0.98 $\mu$mol/g TiO₂ for CoPc and 0.86 $\mu$mol/g TiO₂ for ZnPc, nearly independent of the amount of TiO₂ used. These newly obtained heterogeneous photocatalysts were employed in the photocatalytic degradation of 4-chlorophenol(4-CP), chlorobenzene(CB) and 1,2,4-trichlorobenzen(TCB) in aqueous media under visible irradiation. Gas chromatography-mass spectrometry (GC-MS) was used for quantitation. The new photocatalysts showed excellent activities with visible-region irradiation in the photocatalytic degradation of persistent organic pollutants (POPs) as compared to the control experiments used with untreated TiO₂ and the difference was attributed to the cooperation of the two elements, namely TiO₂ and MPc. Experiments show that in two hours nearly complete degradation of POPs were observed.

Herein, we report photochemical hydrogen evolution systems consisting of various rhodium based catalysts with Wilkinson type structures, Zn metalated porphyrins and fluorescein as photosensitizers and triethanolamine as a sacrificial electron donor in acetonitrile/H₂O (1:1) solution. Since rhodium complexes 1 and 2 are used for the first time as catalysts in this type of systems, a systematic study was performed in order to elucidate the best conditions for H₂ production. Upon visible irradiation hydrogen production was detected and the best results were obtained at pH 7 when dye P3 and catalyst 1 were used with a TON of 61, after 48 h and in the presence of dye P1 and catalyst 2 with a TON of 69, after the 48 h.

A new copper phthalocyanine, namely 9(10),16(17),23(24)-tri-tert-butyl-2-[acetynyl-(4-carboxy)phenyl]phthalocyaninatocopper and its related free base have been synthesized as potential stable blue dyes for dye sensitized solar cells. The molecule structure consists on an unsymmetrically-substituted macrocycle bearing three tert-butyl groups and one phenylethynyl moiety as peripheral substituents and it is analogue to that of a previously published zinc derivative. Chemical and optical characterizations, as well as theoretical calculations of the frontier orbitals of both molecules are discussed. To evaluate the effect of the central metal on the photovoltaic behavior of this dye, the novel molecules have been both tested and confronted with the zinc derivative. This last one has shown efficiency values significantly higher than those previously published with a 2.10% maximum efficiency, while the other two dyes yielded 1.66% and 1.38% maximum efficiency respectively.

A series of tetraphenyl meso-substituted porphyrins with either p-amino or p-carboxy substituents has been studied as dyes for standard dye-sensitized solar cells (DSSCs). The porphyrins with greater numbers of amino groups generally show greater efficiency, primarily due to higher photocurrents; open-circuit voltage and fill factors are comparable. The most efficient sensitizer was the trans disubstituted zinc porphyrin, with an overall solar energy conversion efficiency of 5.66%, slightly higher than the triamino zinc porphyrin at 5.18%. The improved efficiency is attributed to the well known push–pull effect in porphyrinsensitized DSSCs with electrondonating groups opposite to the electronwithdrawing anchoring (carboxy) groups. It is suggested that porphyrin derivatives with cis diaminophenyl groups show somewhat diminished efficiency due to difficulties with regeneration of the dye from its oxidized form.

We attempted the calculation of an accurate equilibrium constant for the dimerization process of enantiomerically pure Zn-1 using UV-vis dilution experiments. At millimolar concentration Zn-1 is involved in a chemical exchange process between its monomeric and dimeric state that is slow on the ¹H NMR timescale. We performed variable-temperature ¹H NMR experiments in CDCl₃ solution to determine the dimerization constant value at different temperatures and performed a van’t Hoff plot to derive the thermodynamic parameters of the process. The calculated thermodynamic data revealed that the dimerization process is entropy-driven and enthalpically opposed. We also probed the coordination of quinuclidine, 1-azabicyclo[2.2.2]octane, 2, to the Zn-1 using UV-vis and ¹H NMR titrations in CDCl₃ solution. At micromolar concentration the Zn-1 exclusively exists in solution as a monomer and forms a simple 1:1, $2\cdot Zn-1$, complex with quinuclidine having a stability constant of $K$($2\cdot Zn-1$) $=$ 10⁶ M${}^{-1}$. On the other hand, the ¹H NMR titrations carried out at 298 K and at millimolar concentration showed that Zn-1 was present in solution as the dimer and formed 1:2, $2\cdot {[Zn-1]}_2$, and 2:2, $2_2\cdot {[Zn-1]}_2,$ complexes by coordination to 2. In addition, the 1:1 complex, $2\cdot Zn-1$ showed a reduced dimerization constant compared to the uncoordinated parent monomer Zn-1. At high quinuclidine concentration, the 1:1 complex, $2\cdot Zn-1$, derived from the coordinated dimer dissociation was also detected. The ¹H NMR spectra of the titrations displayed separate signals for some hydrogen atoms of the Zn-phthalocyanine in each one of the four species. Remarkably, the chemical exchange processes involving free and bound quinuclidine in the monomeric and dimeric complexes showed different kinetics on the NMR timescale.

The synthesis of new metalated diporphyrinylamines is described. The electronic ≪communication≫ through the amino function linking the two porphyrins was clearly demonstrated by electronic spectroscopy. In addition, intramolecular magnetic interactions were measured between two copper(II) ions located in the two linked porphyrins. Compared to the reported value ($J\sim$ -2 K) for Osuka’s triply fused bis-copper(II) porphyrin dimer, a relatively high antiferromagnetic coupling constant was determined in our compound ($J$ = -11 K).

The liquid or low-melting free base corroles (A₂Bcor)H₃ with cor $=$ trianionic macrocyclic core without any protons, A $=$ 4-(OC${}_{12}$H${}_{25})$C₆F₄ and B $=$ 3,4,5-(OC${}_{12}$H${}_{25}{)}_3$C₆H₂ for 4 or $=$ 3,4,5-(OC${}_{18}$H${}_{37}{)}_3$C₆H₂ for 5, were prepared in a straightforward manner from 3,4,5-trialkoxybenzaldehydes and a suitable dipyrrane possessing four fluorine atoms. This synthetic result paved the way to stable and at the same time liquid or low melting meso-substituted corroles. The presence of altogether eight fluorine atoms in the trans-A₂B-corroles was essential to maintain corrole stability. An electrochemical study of 4 in CH₂Cl showed that the behavior of this corrole is dominated by three different species in an acid base equilibrium with each other: [(A₂Bcor)H₂]${}^{-}$, 4${}^{-}$, (A₂Bcor)H₃, 4 and [(A₂Bcor)H₄]${}^{+}$, 4${}^{+}$. Four different redox states for each of these three components could be identified in 12 separate one-electron transfer redox processes. A mechanism explaining the observed twelve redox and four chemical steps is proposed. Differential scanning calorimetry measurements have proven that if alkyl chains are long enough (C18), the corrole melts at record low temperature (63.7 ${}^{\circ }$C) and it is stable throughout multiple temperature variation cycles up to 300 ${}^{\circ }$C. Upon crystallization an initial kinetic driven crystal packing for the product is obtained that melts at 20 ${}^{\circ }$C, but after sufficient time has elapsed (20 h), it converts into the thermodynamically stable crystal packing form with melting point of 63.7 ${}^{\circ }$C, probably because of rearrangements in the alignment of the five OCH${}_{18}$H${}_{37}$ chains in 5.

A star-shaped array, consisting in four tetraphenylporphyrin fused to a phthalocyanine central unit by pyrazine groups, is constructed via the condensation reaction of a dicyanoquinoxaline annulated to a porphyrin ring. The nature of the annulated group is critical for the success of the reaction; in the case of smaller linkers, such as a dicyanopyrazine unit, a nucleophilic substitution occurred, giving the corresponding alcoxy derivative in alcoholic solvents. The visible spectrum of the array shows the typical absorptions of the macrocyclic sub units. The synthetic pathway here presented opens the way to the preparation of $\beta$-fused porphyrin-phthalocyanine arrays.

Formation of self-assembled monolayers (SAMs) of three porphyrin and one phthalocyanine derivatives on thin ZnO film was studied by monitoring absorption spectra of the samples. The compounds were equipped with carboxylic or phosphate groups to bind to the surface. The SAM formation was found to be fast. The layer was formed in less than 15 min for all studied porphyrins, and 30 min was sufficient to form phthalocyanine layer. For porphyrins with different anchor groups the SAM formation was too fast to see any difference between the anchoring groups. The stability of SAMs was tested then by immersing the samples into neat solvents. Upon immersion the SAMs were gradually losing the absorbance for all the compounds with degradation trends being in line with p$K_a$ values of the binding groups of the same type. However, even for the weakest binding group the SAM was relatively stable after a few tens of minutes of washing, which was sufficient to remove physisorbed compounds but the SAM was essentially not destroyed. Comparison of SAMs on thin films with SAMs on ZnO nanorods and TiO₂ nanoparticle films indicated the same fast layer formation but relatively weaker SAMs stability, showing 20–40% faster absorption losses during the washing.

Hierarchical self-assembly of porphyrins is an intrigue research field, which can lead to the design of functional materials. Porphyrin derivatives self-assembling under hierarchical control allows to understand the principles governing molecular recognition processes, as demonstrated for meso-tetrakis(4-phosphonatophenyl)porphyne (H₂TPPP) whose polyprotic nature is responsible for a pH-dependent hierarchical aggregation. Herein, self-assembly of meso-tris(4-phosphonatophenyl)corrole (TPPC) in aqueous solution has been spectroscopically studied and compared to that of TPPP. The corrole aggregation does not follow the hierarchical rules that govern the porphyrin counterpart due to the accessibility of the core of the macrocycle to protons, promoted by the reduced number of involved intermolecular H-bonds.

Unprecedentedly large subporphyrazines (SubPz) with dibenzoquinoxalino-fusion and peripheral phenyl substitution were prepared by the cyclization of perfluorated or non-fluorous polyphenyl-substituted quinoxaline dinitriles and characterized by spectroscopic techniques. The compounds suitability to act as photosensitizers was explored by wavelength-specific induction of singlet oxygen luminescence and was shown to be excellent. Determination of ¹O₂-quantum yields suggests that fluorine substitution enhances the photosensitization efficiencies of the SubPz. On the other hand, cyclic voltammetry reveals an increase of irreversible reductive processes in case of the fluorinated SubPz.

Two A₂B mono-cobalt corroles and the corresponding bis-cobalt derivatives linked by a xanthene acyl group were synthesized, characterized as to their electrochemistry and spectroelectrochemistry in nonaqueous media and then examined as catalysts for the electroreduction of O₂ in 1.0 M HClO₄. The investigated mono- and bis-corroles are represented as (NH₂Ph)(YPh)₂CorCo(PPh${}_3)$ and [(YPh)₂CorCo(PPh${}_3)$]₂Xac, respectively, where Cor is the trianion of the corrole, Y is a CH₃ or Cl substituent on the para-position of the 5- and 15-meso-phenyl rings of the macrocycle and Xac is the xanthene acyl group linking the two macrocycles in a face-to-face arrangement. The neutral compounds were characterized by cyclic voltammetry while thin-layer spectroelectrochemistry was used to elucidate UV-visible spectra of the compounds in their electrooxidized or electroreduced forms. Rotating disk and rotating ring-disk electrode measurements were also utilized to examine the electrocatalytic activity for reduction of O₂ when the face-to-face corroles were adsorbed on the electrode surface in 1.0 M HClO₄. The number of electrons transferred in the catalytic electroreduction of dioxygen was calculated from currents at the disk electrode using Koutecky–Levich plots. The effect of linking the two cobalt corrole macrocycles on UV-visible spectra, redox potentials and electrocatalytic activity for the reduction of dioxygen is discussed.

This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-$n$-butoxyphthalocyanine 1H${}_2$ and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. ¹H NMR investigations evidenced of higher dissymmetry of electronic density in 1H${}_2$ in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[${\chi }^{(3)}$]/$\alpha$, ${\beta }_{eff}$, and $\gamma$ for 1H${{}_2}_{}$in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[${\chi }^{(3)}$]/$\alpha$ values of the order of 10${}^{-11}$ in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H₂[(BuO)₈Pc]. NLO properties of 1H${}_2$ were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[${\chi }^{(3)}$]/$\alpha$ was almost three times higher in comparison with 1H${}_2$ solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation.

With the aim of assessing the role of the chemical structure of the photosensitizer on the photophysical and photochemical properties of the final nanoparticle suspension, we have investigated a series of poly-(ethylene glycol)-poly-($D,L$-lactide-co-glycolide) nanoparticles containing a hydrophobic or a hydrophilic porphyrin covalently conjugated to the nanoparticle. Covalent conjugation responded to the objective of trying to improve photosensitizer loading in these nanoparticles, especially for hydrophilic photosensitizers, but also enabled the porphyrins to remain attached to the nanoparticle without necessarily being inside the poly-($D,L$-lactide-co-glycolide) core. This strategy has provided valuable information about the dependence of the photophysical and singlet oxygen photosensitizing properties of the suspensions on the nature of the photosensitizer. It is concluded that poly-($D,L$-lactide-co-glycolide) nanoparticles with covalently-bound hydrophilic porphyrins show superior singlet oxygen photosensitizing ability.

Novel 4,4′-{(diphenylmethylene)bis(4,1-phenylene)bis(oxy)} bridged ball-type metal-free, zinc(II), cobalt(II) and iron(II) ball-type metallophthalocyanines were achieved by the reaction of the bisphthalonitrile derivative in 2-dimetylaminoethanol. The isolation of the metal-free and metallophthalocyanines were carried out by both planar and column chromatography and also by hot soxhalet extraction. Their structures have been characterized by infrared, ultraviolet-visible, ¹H nuclear magnetic resonance and matrix assisted laser desorption/ionization mass spectroscopies. The redox characters of the ball-type metallophthalocyanines have been investigated by cyclic voltammetry, square wave voltammetry, controlled potential coulometry and spectroelectrochemistry in nonaqueous media. The investigation suggested that the ball-type complexes form ring-based and/or metal-based mixed-valence species as a result of the remarkable interaction between the two Pc rings and/or metal centers. Furthermore, these species were found to be stable as evidenced by the splitting of the relevant redox processes. The electrocatalytic oxygen reducing performances of the dinuclear ball-type complexes were also studied. The compound involving Fe(II) centers at the phthalocyanine cores displayed higher catalytic performance towards oxygen reduction than those of other ones. By using these compounds as sensing materials, a flow type quartz crystal microbalance sensor was developed for the detection of small concentrations of heavy metal ions. A cadmium ion sensitivity of 2.85 × 10⁴ Hz/mg.L${}^{-1}$ was observed with ball-type iron(II) phthalocyanine coated quartz crystal microbalance sensor. Detection of other metal ions including Fe${}^{2+}$, Zn${}^{2+}$, Ag${}^{2+}$ and Sn${}^{2+}$ were also performed. The results indicated that 1– 4 functionalized quartz crystal microbalance sensors can be used for the detection of heavy metal ions in aqueous solution. Partition coefficients obtained from the linear response regimes of the calibration curves are in the 8.6 × 10⁴–5.4 × 10⁵ range. Results show that the minor structural difference between metal free and metallophthalocyanine poses significant impact on metal ion partitioning.

A new unsymmetrical phthalocyaninato zinc complex with typical amphiphilic nature, namely 2,3-di(4-hydroxyphenoxy)-9,10,16,17,24,25-hexakis($n$-octyloxy)phthalocyaninato zinc, Zn[Pc(OC₈H${}_{17}{)}_6$(OPhOH)₂], has been designed, synthesized, and characterized by a range of spectroscopic methods. The Langmuir monolayer of this amphiphilic complex has been used as not only an organic template but also as a good functional organic material to produce the monodispersed nanoparticles of Zn[Pc(OC₈H${}_{17}{)}_6$(OPhOH)₂]/ZnS nanocomposite. In addition, multilayer pure and hybrid films have also been obtained by depositing monolayers of the amphiphilic complex and Zn[Pc(OC₈H${}_{17}{)}_6$(OPhOH)₂]/ZnS nanocomposite, respectively, using the Langmuir–Shäfer (LS) method. Surface pressure-area isotherms, UV-vis spectroscopic, and XRD studies indicate that the molecules adopted a face-to-face configuration and edge-on orientation in both the multilayer pure LS and Zn[Pc(OC₈H${}_{17}{)}_6$(OPhOH)₂]/ZnS hybrid films. In particular, current–voltage (I–V) measurements reveal the superior conductivity of the Zn[Pc(OC₈H${}_{17}{)}_6$(OPhOH)₂]/ZnS hybrid film nanocomposites to that of the stand-alone films, and this is due to the existence of the densely packed molecular architecture in the film matrix and the large interfacial area between the two components. These characteristics remove the charge transporting bottleneck by creating an interpenetrating consistent thin film of hybrid materials. The result sheds lights on new ways for developing organic-inorganic hybrid nanostructures with good semiconducting properties.

Steroids linked to porphyrin fluorophores are being developed to improve the selectivity of photosensitizers for photodyanamic therapy and fluorescence imaging of steroid-hormone positive cancers. A number of porphyrin derivatives substituted with one or two steroid moieties coupled via a 17$\alpha$-ethynyl group of estradiol, testosterone and 19-nortestosterone were synthesized using Pd(II) as a catalyst.

Porphycene dimers connected by $m$-phenylene (DPc– m P) and 2,5-thienylene (DPc–T) linkages have been synthesized from 2,7,12,17-tetrahexyl-3-iodoporphycene by palladium-catalyzed cross-couplings. The crystal structures of porphycene dimers revealed that meta-phenylene linkage provides a highly twisted structure with the dihedral angel of 103° between two porphycene units, while thienylene linkage provides a nearly planar structure of two porphycene units. These porphycene dimers showed strong absorption thorough the visible to NIR regions and HOMO and LUMO energy levels of them are suitable as $n$-type materials of organic solar cells (OSCs) in combination with P3HT as a $p$-type material. The hole and electron mobilities of the blended films of the porphycene dimers and P3HT obtained by space-charge-limited-current (SCLC) method were 3.7 × 10${}^{-4}$ and 0.26 × 10${}^{-4}$ cm².V${}^{-1}$.s${}^{-1}$ for DPc– m P :P3HT, and 3.2 × 10${}^{-4}$ and 0.027 × 10${}^{-4}$ cm².V${}^{-1}$.s${}^{-1}$ for DPc–T :P3HT. Atomic force microscopy (AFM) and thin-film X-ray diffraction analysis (XRD) measurements indicated that the blended films of the porphycene dimers and P3HT formed amorphous films with smooth and low-roughness surfaces, whereas the blended film of porphycene monomer and P3HT created the highly crystalline film with huge domain structures. The OSCs composed of porphycene dimers and P3HT showed power conversion efficiencies of 0.08% was twice as high as that of monomer-based OSC.

A new carboxy-Zn(II)phthalocyanine bearing rigid 2,6-diarylphenyl peripheral substituents linked to the macrocycle through alkynyl spacers has been prepared by a convergent approach, which implies a triple Sonogashira coupling between the formyltriiodoZnPc and the corresponding terminal alkyne. Indeed, the introduction of this type of $\pi$-conjugated peripheral substituents accounts for a remarkable red shift of the phthalocyanine Q-band until ca. 700 nm. However, aggregation phenomena could not be supressed and may explain the moderate overall efficiencies achieved with these devices.

Herein, we report the synthesis of two amphiphilic porphyrins having pyridinium moieties and their anion recognition properties in aqueous medium. The study of their interactions with various anions reveals that these porphyrins exhibit unique and selective interactions with CN^- ions when compared to the other anions. The addition of CN^- ions to an aqueous solution of the butyl porphyrin resulted in a hypochromicity of ca. 78% at 419 nm with a concomitant band formation at 449 nm in the absorption spectrum. Similarly, we observed ca. 82% quenching in the emission intensity by the addition of 12.5 M of CN^- ions in the fluorescence spectrum of the porphyrin mediated through aggregation. The limit of detection of CN^- ions was found to be ca. 49 ppb and the nature of interactions has been studied through various microscopic and spectroscopic techniques. These studies have confirmed 1,4-addition of CN^- ions to the pyridinium moiety of the porphyrin system, which led to the aggregation induced self-assembly resulting in the sensitive detection of CN^- ions through changes in absorbance and fluorescence intensity in aqueous medium.

5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin reacts with primary alkylamines and heterocyclic amines, at 50°C and under high pressure (450 MPa), to produce the $N$-substituted tetraamino derivatives in high yields. Under similar conditions, the reaction with the bulky dibutylamine and dipentylamine affords the corresponding mono-substituted dialkylaminoporphyrins in 10% yield. This new protocol arises as a considerable improvement of the methods already known, which usually require high temperatures and are not effective when using secondary amines having long alkyl groups.

The use of metallo-phthalocyanines (MPcs) in many technological applications requires the development of specific methods for flexible thin film fabrication. An interesting and simple strategy is the physical encapsulation of MPcs within viscoelastic gel scaffolds. However, non-covalent incorporation of large external molecules into gel networks is a challenge because the balance between dissolution and crystallization in metastable gel phases is likely to be altered changing the properties and/or stability of the material and, therefore, threatening its functionality. In this work, we report preliminary results regarding non-covalent inclusion of MPcs into different gel networks and the effects on their thermal, morphological and mechanical properties. In general, slight variations on the $T_{gel}$were observed for most combinations prepared at well-defined concentrations in the presence of suitable MPcs, except for the organogel made of peracetylated $\alpha$-cyclodextrin and the hydrogel made of a bile acid-based gelator. These gels experienced a remarkable enhancement of the $T_{gel}$ of ca. 20°C with respect to the pristine gels. Moreover, preservation of monomeric dye species and reduced photodegradation was also observed in some hybrid gels. Relative correlations between thermal stability, morphological features and mechanical properties were also drawn during the study. Maintenance of the catalytic activity of a CuPc immobilized in a supramolecular gel network was also demonstrated by the aerobic oxidation of benzhydrol to benzophenone at room temperature.

We report the synthesis, redox and photo-physical properties, as well as singlet oxygen reactivity of the first representatives of Group III perfluoroalkyl perfluoro metal phthalocyanines, gallium and indium complexes. Microwave-assisted synthesis was used to produce F${}_{64}$PcM, M $=$ Ga, In in reasonable yields. Both Ga and In complexes exhibit high thermal and chemical stability properties, attributed to the perfluoroalkyl perfluoro phthalocyanine ligand. Electrochemical and spectroelectrochemical measurements show reversible redox processes for both compounds, including spontaneous re-oxidations following electrochemical or photochemical reductions. No electrochemical or chemical oxidations of the neutral complexes are observed. Photo-hydroperoxidation of ($S)$-(-)-citronellol occurs with rates of 13.5 and 1.7 $\mu$mol O₂ min${}^{-1}$ mol${}^{-1}$ Pc and substrate turnovers of 225 and 28.2 mmol ($S)$-Cit s${}^{-1}$ mol${}^{-1}$ Pc for the In and Ga complexes, respectively. The solid state materials are stable and can be sublimed at temperatures higher than 380°C. Related complexes are candidates for similar chemistry and photophysics based on the observation that the fluorinated ligand determines most of the favorable properties.