Expansion and contraction: Shaping the porphyrin boundary via diradical reactivity

  title={Expansion and contraction: Shaping the porphyrin boundary via diradical reactivity},
  author={Leigh J K Boerner and David F. Dye and Tillmann Koepke and Jeffrey M. Zaleski},
  journal={Coordination Chemistry Reviews},
Synthesis and antiaromatic character of alkyl-substituted di-peri-dinaphthoporphyrin Ni(II) complex
Antiaromatic molecules have recently been proven to display unique properties such as small HOMO–LUMO gaps, ambipolar carrier transporting and π-stack-induced aromatic stabilizations. These
Carbene functionalization of porphyrinoids through tosylhydrazones.
The method for carbene functionalization of porphyrinoids through thermal decomposition of their tosylhydrazones created a new synthetic pathway for tailoring the perimeter of tetrapyrrolic macrocycles and allows the obtainment of dyes with controllable spectral optical properties.
Porphyrin Macrocycle Modification: Pyrrole Ring-Contracted or -Expanded Porphyrinoids
These porphyrin derivatives have recently gained an increasing interest due to their potential application in PDT, as multimodal imaging contrast agents, NIR-absorbing dyes, optical sensors for oxygen, cyanide, hypochlorite and pH, and in catalysis.
Bioinspired Orientation of β-Substituents on Porphyrin Antenna Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity.
This work introduced a bioinspired approach by orientation of β-dilactone moieties on porphyrinates to modulate the energy transfer process from the lowest triplet excited state of the ligand (T1) to the emitting level of ytterbium(III) (2F5/2, Yb*).
Anion Control of Lanthanoenediyne Cyclization.
A Bergman cyclization landscape that is influenced by the bonding of metal to an enediyne ligand but whose reaction barrier is ultimately dominated by the coordinating ability of the accompanying anion.
Synthesis, Structures, and Near-IR Absorption of Heterole-Fused Earring Porphyrins.
A reaction sequence of regioselective peripheral bromination, Suzuki-Miyaura coupling with 2-borylated thiophene or pyrrole, and oxidative ring-closure with FeCl3 allowed the synthesis of
Synthesis of Di-peri-dinaphthoporphyrins by PtCl2 -Mediated Cyclization of Quinodimethane-type Porphyrins.
Di-peri-dinaphthoporphyrins can be regarded as a key and common substructure of fused porphyrinoids, which exhibit characteristic paratropic ring currents that presumably arise from 24π antiaromatic circuit as a dominant resonance contributor.
Photoactivated Transition-Metal Triggers for Ambient Temperature Enediyne and Dienyne Cyclization: Ruthenium-η6-Naphthalene Complexes
A persistent challenge confronting potential applications of the Bergman cycloaromatization reaction is the development of methods for spatiotemporal control of diradical formation. Photochemical
Carbene-Type Species in the Functionalization of Porphyrin Derivatives
Carbenes and NHCs play an important role in porphyrin chemistry and several synthetically useful transformations leading to the preparation of new porphyrin derivatives have been developed. This
Macroheterocyclic μ-Nitrido- and μ-Carbido Dimeric Iron and Ruthenium Complexes as a Molecular Platform for Modeling Oxidative Enzymes (A Review)
Recent scientific publications demonstrate a new approach to modeling catalysts that mimic heme-containing enzymes. It involves the use of μ-oxo, μ-nitrido, and μ-carbido dimeric transition metal


Gating the mechanistic pathway to the elusive 4-membered ring azeteoporphyrin.
A model is presented showing that azeteoporphyrin formation via the Wolff rearrangement is dependent upon the structural disposition of the adjacent framework, and the specific reaction intermediate formed is very sensitive to this feature.
Expansion by contraction: diversifying the photochemical reactivity scope of diazo-oxochlorins toward development of in situ alkylating agents.
The ability of these chromophores to photochemically react under substrate control may make unimolecular porphyrinoid photoreagents such as these useful for applications in photobiology or O2-independent photodynamic therapy.
Porphyrins with exocyclic rings. 16. Synthesis and spectroscopic characterization of fluoranthoporphyrins, a new class of highly conjugated porphyrin chromophores.
The utility of aromatic ring fusion in altering the properties of porphyrinoid systems is demonstrated by a series of fluoranthoporphyrins synthesized, which showed many of the same spectroscopic features, although the presence of two ring fusions gave rise to an increase in theSpectroscopic shifts.
Porphyrins with Exocyclic Rings. 11.1 Synthesis and Characterization of Phenanthroporphyrins, a New Class of Modified Porphyrin Chromophores
To obtain insights into the factors that influence the electronic spectra of conjugated porphyrin systems, a series of porphyrins with fused phenanthrene subunits have been synthesized.
Synthesis of isomeric angularly annealed dinaphthoporphyrin systems: examination of the relative positioning and orientation of ring fusion as factors influencing the porphyrin chromophore.
Porphyrins built up from two naphtho[1,2-c]pyrrole subunits and two beta-substituted pyrroles can produce five isomeric dinaphthoporphyrin systems, and all five of these systems were synthesized in isomerically pure form.
Synthesis and structural characterization of porphyrinic enediynes: geometric and electronic effects on thermal and photochemical reactivity.
Generation of a common product suggests that both thermal and photochemical pathways to Bergman cyclization in solution contain significant activation barriers to formation of the 1,4-phenyl diradical intermediate, and under these solution conditions, alternate reaction channels are more thermodynamically favorable.
Extending supramolecular fullerene-porphyrin chemistry to pillared metal-organic frameworks
This arranagement identifies the fullerene–porphyrin interaction as a structure-defining element and the same motif is seen in a related ribbon structure having C70 intercalated into HgI2-linked H2TpyTP.
Porphyrins with exocyclic rings. 15.(1) synthesis of quino- and isoquinoporphyrins, aza analogues of the naphthoporphyrins.
A zinc chelate of the isoquinoporphyrin system shows a high degree of regioselective intermolecular interaction/aggregation in chloroform solution that may lead to selectivity in molecular recognition studies.