Themed collection Porphyrins & Phthalocyanines
self-assembly to noncovalent synthesis of programmable porphyrins' arrays in aqueous solution
Fast noncovalent synthesis of programmable porphyrin arrays is facilitated by suitable templates.
Phthalocyanines: a new class of G-quadruplex-ligands with many potential applications
Phthalocyanines as a new class of G-quadruplex-ligands are promising not only for organic electronics but also for biomedical applications.
Porphyrins for dye-sensitised solar cells: new insights into efficiency-determining electron transfer steps
The correlation between molecular structure and efficiency-determining electron transfer steps is highlighted in a series of porphyrin-sensitised TiO2 solar cells.
Blooming of confused porphyrinoids—fusion, expansion, contraction, and more confusion
Recent development of confused porphyrinoids led by fusion, expansion and contraction is briefly introduced.
Novel D–π–A structured Zn(II)-porphyrin
dyes containing a bis(3,3-dimethylfluorenyl)amine moiety for dye-sensitised solar cells
A high photovoltaic efficiency of 7.22% was achieved with a Jsc of 15.30 mA cm-2, a Voc of 669 mV and a FF of 0.71 for 2Flu-ZnP-CN-COOH with a multi-functional co-adsorbent, under 100 mW cm-2 AM 1.5 G simulated light.
metallophthalocyanine 2D covalent organic frameworks: the role of central metals in controlling π-electronic functions
The central metals control the improvement of light absorbance, ease of carrier transport, and gain of photocurrent of phthalocyanine COFs.
heme lyase can mature a fusion peptide composed of the amino-terminal residues of horse cytochrome c
Cytochrome c heme lyase (CCHL) attaches heme covalently to peptides composed of the N-terminal segment of horse cytochrome c fused to a non-heme protein.
photon absorption and its saturation of a self-organized dimer of an ethynylene-linked porphyrin tandem
A self-organized dimer by complementary coordination of ethynylene-linked porphyrin tandems displayed strong two-photon absorption with extension of the π-conjugation system by the terminal phenylethynyl groups. Saturation of the two-photon absorption was also observed due to the intense transition.
Sevenfold enhancement on
porphyrin dye efficiency by coordination of ruthenium polypyridine complexes
Scheme showing the supramolecular porphyrin dye anchored on TiO2 surface stressing the energy transfer and electron injection processes.
Water-soluble ionic benzoporphyrins
Ionic water-soluble tetrabenzoporphyrins were synthesized. UV-Vis absorption spectra displayed red-shifted and broadened Soret bands, and significantly enhanced Q bands.
Structural basis for oxygen sensing and signal transduction of the
heme-based sensor protein Aer2 from Pseudomonas aeruginosa
Trp283 is responsible for oxygen sensing and signal transduction in a chemotaxis signal transducer protein, Aer2.
heme degradation enzyme, HutZ, from Vibrio cholerae
HutZ from Vibrio cholerae was purified and found as heme oxygenase, which degrades heme to release iron essential for bacterial survival.
Porphyrin nanochannels reinforced by hydrogen bonding
Hydrogen bonding among the peripheral carboxyl groups on the saddle-distorted porphyrins strongly linked porphyrin nanochannels to reinforce the supramolecular structures.
Vibrational dynamics of oxygenated
Advanced spectroscopic techniques coupled with DFT calculations reveal the vibrational dynamics of the iron in dioxygen complexes with heme proteins.
Rational design of a
phthalocyanine–perylenediimide dyad with a long-lived charge-separated state
The longest charge-separated state so far, 72 μs, without the addition of external components, for phthalocyanine–perylenediimide arrays has been described.
A new synthetic approach to benzoporphyrins and Kröhnke type porphyrin-2-ylpyridines
Synthesis of new 2-(2,6-diarylpyridin-4-yl)porphyrins, benzoporphyrins and porphyrin–chalcone-type derivatives through a new synthetic methodology catalyzed by La(OTf)3.
Generation and characterization of high-valent iron oxo phthalocyanines
The first high-valent iron oxo complex on the phthalocyanine platform was prepared and characterized by low temperature UV–vis, cryospray MS, EPR, X-ray absorption and X-ray emission methods.
Ruthenium(IV) porphyrin catalyzed phosphoramidation of aldehydes with phosphoryl azides as a nitrene source
[RuIV(por)Cl2] (por = porphyrin dianion) can efficiently catalyze nitrene insertion into aldehyde C–H bonds with phosphoryl azides as a nitrene source to give N-acylphosphoramidates in good to high yields.
Synthesis of stable monoporphyrinate lanthanide(III) complexes without ancillary ligands
A new type of porphyrin ligand bearing four triazole groups at the ortho-positions of phenyl rings in tetraphenylporphyrin was synthesized for the formation of monoporphyrinate lanthanide complexes without ancillary ligands.
Controlled growth of narrowly dispersed nanosize hexagonal MOF rods from Mn(III)–
porphyrin and In(NO3)3 and their application in olefin oxidation
A new class of narrowly dispersed nanosize hexagonal MOF rods from Mn(III)–porphyrin and In(III) was obtained.
Hydrogenation effects in metalloporphycenes: synthesis and redox behavior of Ni(II)–tetra(n-propyl)dihydroporphycene
We have successfully achieved the synthesis and characterization of 2,3-dihydro-2,3,12,17-tetrapropylporphycene 1 and its NiII complex 2.
Dinuclear single-molecule magnets with
porphyrin– phthalocyanine mixed triple-decker ligand systems giving SAP and SP coordination polyhedra
Two terbium ions in a porphyrin–phthalocyanine mixed triple-decker complex have shown sharply different magnetic behaviours depending on their local symmetry.
Modular self-assembled multiporphyrin cages with tunable shape
Combination of a single flat bis-zincporphyrin metallacycle with different polytopic N-linkers leads, with a limited synthetic effort, to the quantitative formation of neutral supramolecular multiporphyrin cages of distinct shape and size.
Structure–charge transport relationship of 5,15-dialkylated porphyrins
5,15-Dialkylated porphyrins were synthesized and characterized. N-Butyl substituted porphyrin leads to the highest thin film crystallinity and best thin film transistor performance with charge carrier mobility up to 3 × 10−2 cm2 V−1 s−1.
Metal-mediated self-assembly of tetrapyridyl porphyrins by Na+ ions
Upon interaction with Na+ ions in CH2Cl2, tetra(4-pyridyl)porphyrin and some of its metallo-derivatives spontaneously form solid deposits on glass, consisting of very regular supramolecular architectures with long-range order and tunable morphologies.
Magneto-chiral dichroism of artificial light-harvesting antenna
We have succeeded in observing the magneto-chiral dichroism of artificial light-harvesting antenna for the first time.
zinc porphyrin-based molecular probe for the determination of contamination in commercial acetonitrile
A zinc porphyrin-based receptor containing four triazole groups at the ortho-position of each phenyl group (1) was utilized as a useful probe for the determination of contaminants in acetonitrile (MeCN). Through the simple observation of the absorption spectrum of 1 in MeCN, the cyanide contamination concentration could be directly determined.
Towards enhancing light harvesting—
subphthalocyanines as electron acceptors
We have demonstrated the unique light harvesting and electron accepting features of dodecafluorosubphthalocyanine covalently linked to extended TTFs.
Interior aliphatic C–H bond
activation on iron(II) N-confused porphyrin through synergistic nitric oxide binding and iron oxidation
Nitric oxide coordination assisted oxidative C–H bond activation on the inner methyl group of iron N-confused porphyrin has been achieved.
Toward aceneporphyrinoids: synthesis and transformations of palladium(II) meso-anthriporphyrin
meso-Anthriporphyrin belongs to the emerging group of aceneporphyrins. A noticeable parallel exists in coordination properties of meso-anthriporphyrin and its lower benzologues, p-benziporphyrin and 1,4-naphthiporphyrin, toward palladium(II).
Enantioselective recognition by a highly ordered
porphyrin- assembly on a chiral molecular gel
Enantioselective recognition of amino acids was achieved by using a highly ordered chiral assembly of achiral porphyrin on a chiral molecular gel. Exceptionally high enantioselectivity was observed for histidine derivatives by monitoring the CD patterns and fluorescence quenching, KSV (L): 26.3 × 103 M−1; KSV (D)-enantiomer: 7.03 × 103 M−1.
Hierarchical cooperative binary ionic
Grafting nanocrystals of one ionically self-assembled cooperative binary ionic solid onto a substructure of another provides multifunctional hierarchical nanocomposites.
Controlled generation of singlet oxygen by a water-soluble meso-pyrenylporphyrin photosensitizer through interaction with DNA
The activity of singlet oxygen generation photosensitized by an electron donor-connecting water-soluble porphyrin can be controlled through interaction with DNA.
The first TDDFT and
MCD studies of free base triarylcorroles: A closer look into solvent-dependent UV-visible absorption
The absorption spectra of several free base triarylcorroles were investigated by MCD spectroscopy.
Facile synthesis of a flexible tethered
porphyrin dimer that preferentially complexes fullerene C70
A porphyrin dimer linked by a flexible tether preferentially binds C70 over C60 in toluene and deposited on glass.
Intramolecular hydrogen bonding as a synthetic tool to induce chemical selectivity in acid catalyzed
A straightforward procedure based on the formation of intramolecular hydrogen bonds to impart selectivity in the preparation of multi-functionalized porphyrins has been developed.
Formation and photoinduced processes of a self-assembled
subphthalocyanine– porphyrin– phthalocyanine supramolecular complex
For the first time, the formation of a 1 : 1 : 1 host–guest–host complex between a cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a cyclodextrin-conjugated phthalocyanine, which exhibits light-harvesting properties, was shown.
Effects of protonation of pyridine moieties on the 2D assembly of
porphyrin layers on Au(111) at electrochemical interfaces
Zinc(II) tetrakis(2-pyridyl)porphyrin, driven by the protonation of the pyridine groups, can provide a characteristic assembly with the alternate inverted form of the pyridine ring at a trans-position on an Au(111) surface.
A bifunctional catalyst for carbon dioxide fixation: cooperative double activation of epoxides for the synthesis of cyclic carbonates
A bifunctional catalyst showed a high turnover number for the synthesis of cyclic carbonates from CO2 and epoxides under solvent-free conditions.
High-order tunneling processes in single-
Cotunneling and the Kondo effect are observed within a single molecule transistor (SMT) device incorporating cobalt-porphyrins at 4.2 K.
Highly reactive meso-like positions of dipyrihexaphyrin
Dipyrihexaphyrin, a porphyrin analogue with a very high reactivity of the meso-like position from sp2 to sp3.
Corrin ring-induced redox tuning
The DFT calculations suggest that the systematic expansion of the corrin macrocycle's N4 core by 0.06–0.10 Å leads to an appreciable lowering of 100–150 mV vs. saturated calomel electrode in the reduction potentials of B12 cofactors. This indicates that the electrochemical behavior of B12 cofactors is tunable in nature which may be relevant to the electron transfer-based activation mechanism for B12-dependent enzymes.
Preparation and structural control of metal coordination-assisted supramolecular architectures of
porphyrins. Nanocubes to microrods
A new series of metal coordination-assisted porphyrin architectures such as nanocubes, nanorods and microrods were successfully synthesized by controlling the synthetic conditions.
Highly enantioselective intermolecular
carbene insertion to C–H and Si–H bonds catalyzed by a chiral iridium(III) complex of a D4-symmetric Halterman porphyrin ligand
Chiral iridium porphyrin [Ir((−)-D4-Por*)(Me)(EtOH)] exhibits excellent reactivity and stereoselectivity towards carbene insertion to C–H and Si–H bonds, affording corresponding products in high yields and enantioselectivities.
Porphyrin-LEGO®: synthesis of a hexafullereno-diporphyrin using
porphyrins programmed for [4+2]-cycloaddition
Porphyrin-LEGO® provides a route to a diporphyrin that functions as a ‘programmed’ scaffold for further [4+2]-cycloaddition of six C60-fullerenes.
A zinc gable
phthalocyanine and a derived planar bis-phthalocyanine containing a shared anthracene unit
A gable-type zinc phthalocyanine and a derived planar bis-phthalocyanine containing a shared anthracene unit have been synthesized and their spectroscopic properties examined.
fluorene-modified porphyrin for efficient dye-sensitized solar cells
A fluorene-modified zinc porphyrin shows efficient dye-sensitized solar cell performance.
Azaphthalocyanines with fused triazolo rings: formation of sterically stressed constitutional isomers
Formation of constitutional isomers of triazolo-fused azaphthalocyanines in relation to the bulkiness of peripheral substitution is described together with a short introduction into their spectral, photophysical and photochemical properties.
oxidation of alcohols by a carbon-supported Rh porphyrin
A Rh porphyrin on carbon black was shown to catalyze the electro-oxidation of aliphatic and benzyl alcohols at very low overpotentials.
A doubly 2,6-pyridylene-bridged
porphyrin– perylene–porphyrin triad
A doubly 2,6-pyridylene-bridged porphyrin–perylene–porphyrin triad was synthesized, which captures a tetrakis(3-pyridyl)porphyrin guest in a 2 : 1 manner.
Molecular engineering and
solvent dependence of excitation energy hopping in self-assembled porphyrin boxes
Excitation energy hopping in self-assembled porphyrin boxes.
Unveiling the three-dimensional structure of the green pigment of
Crystal structural analysis of the green pigment of nitrite-cured meat reveals that sterics control the regiospecificity of heme 2-vinyl nitration.
Competitive inhibition of a metal-free porphyrin oxygen-reduction catalyst by water
Competitive inhibition of the diprotonated tetraphenylporphyrin oxygen-reduction catalyst by water is reported and linked to the DFT free energy of extraction of oxygen, water, and reactant acid anion from the porphyrin complex.
Synthesis and properties of β,β-sp3-hybridized
A β,β-sp3-hybridized subphthalocyanine analogue was synthesized, and its split Q bands in longer and shorter wavelength regions relative to subphthalocyanines were revealed.
Non-covalent versus covalent donor–acceptor systems based on near-infrared absorbing azulenocyanines and C60
Supramolecular and covalent Zn–azulenocyanine–C60 systems, which exhibit a remarkable panchromatic absorption, have been prepared and their photophysical properties studied.
Induction of supramolecular chirality in di-zinc(II) bisporphyrin via tweezer formation: synthesis, structure and rationalization of chirality
Two new complexes consisting of an achiral bisporphyrin host and a chiral diamine guest are reported. One shows a remarkably high amplitude bisignate CD signal while the other one shows a very low value. The origin of chirality has been rationalized.
Colorimetric detection of trace
water in tetrahydrofuran using N,N′-substituted oxoporphyrinogens
Oxoporphyrinogens bind water molecules leading to visible colour changes due to variation in π-electronic structure. One of the OxP derivatives is a colorimetric indicator of trace water in THF.
Antioxidant-substituted tetrapyrazinoporphyrazine as a fluorescent sensor for basic anions
Tetrapyrazinoporphyrinazine substituted at its periphery with eight antioxidant 3,5-di-t-butyl-4-hydroxyphenyl groups behaves as a fluorescent sensor for fluoride anions.
Synthesis of 5,10,15-triazaporphyrins—effect of benzo-annulation on the electronic structures
Reactions of 1,9-dibromodipyrromethene and 1,3-diiminoisoindolines provided dibenzo-5,10,15-triazaporphyrins exhibiting intense Soret and Q bands due to their hybrid properties between porphyrins and phthalocyanines.
Metal centre effects on HNO binding in
porphyrins and the electronic origin: metal's electronic configuration, position in the periodic table, and oxidation state
Several general HNO binding trends with respect to metal centre characteristics and a common electronic origin were discovered.
Spectroscopic capture and reactivity of S = 1/2 nickel(III)–oxygen intermediates in the reaction of a NiII-salt with mCPBA
Elusive Ni(III)–O(H) species are trapped and shown to be active oxidants in oxygen atom transfer and C–H bond activation reactions.
Translocation-coupled transmetalation at the origin of a dinuclear lead
porphyrin complex: implication of a hanging-atop coordination mode
The formation and solid state characterization of an unprecedented bimetallic lead porphyrin complex are described.
Light-to-electron converting panchromatic supramolecular solar cells of
phthalocyanine– porphyrin heterodimers adsorbed onto nanocrystalline SnO2 electrodes
An elegant approach of decorating tetrapyrrole macrocycles having different absorption characteristics, electrostatically stacked onto the SnO2 surface as wide-band capturing supramolecular solar cells is reported.
Excitonic coupling interactions in the self-assembly of perylene-bridged bis(β-cyclodextrin)s and porphyrin
Strong excitonic coupling was achieved with the self-assembly of perylene-bridged bis(b-cyclodextrin)s and water-soluble porphyrin through hydrophobic interactions.
Unexpected formation of the nickel seco-tribenzoporphyrazine with a tribenzotetraazachlorin-type absorption spectrum
Minor products in the reaction between substituted 1,3-diiminoisoindolines and 2,5-diamino-3,4-dicyanothiophene were identified as the nickel seco-tribenzoporphyrazines 4 and 5.
Porphyrin and phthalocyanine glycodendritic conjugates: synthesis, photophysical and photochemical properties
Synthesis, photophysical and photochemical features of novel water soluble galactodendrimeric-porphyrin and -phthalocyanine conjugates, incorporating a carbohydrate shell of eight and sixteen D-galactopyranose units, respectively.
S2 emission from chemically modified BODIPYs
BODIPY showed anomalous S2 emission from the second excited state (S2) at shorter wavelength. The photodynamics of the S2 state was investigated by fluorescence up-conversion and transient absorption spectroscopic measurements.
Synthesis of stable free base secochlorins and their corresponding metal complexes from meso-tetraarylporphyrin derivatives
Cleavage reactions of 2,3-diamino-meso-tetraarylporphyrins and meso-tetraarylporphyrins fused to imidazole rings afforded secochlorins, including stable free base derivatives.
Organometallic multiads of zinc(II)
porphyrins with interchromophoric cooperativity in S1 and T1 energy transfers
Three different S1 and T1 energy donors are linked onto a central zinc(II) porphyrin acceptor and energy transfer rates show cooperativity.
An artificial photosensitizer
drug network for mitochondria-selective photodynamic therapy
A multimeric chlorin e6 network with cleavable disulfide linkages allowed for improved mitochondria uptake and tumor inhibition.
About this collection
The peer-reviewed articles in this ChemComm web themed issue highlight recent cutting-edge achievements in the areas of porphyrins, phthalocyanines and related macrocyclic compounds.
The guest editors of this issue are Jonathan Sessler (University of Texas at Austin), Penny Brothers (University of Auckland) and Chang-Hee Lee (Kangwon National University).
Articles in this web themed issue will be added below as soon as possible after they are published.