An Electron‐Deficient Porphyrin Tape

Hexakis(pentafluorophenyl)‐substituted meso–meso‐linked Zn^II–diporphyrin ( 9 ), which was prepared by the acid‐catalyzed cross‐condensation of 1,1,2,2‐tetrapyrroethane ( 5 ) with dipyrromethane dicarbinol ( 6 ), was converted into meso–meso,β‐β,β‐β triply linked Zn^II–diporphyrin 3 by oxidation with 2,3‐dichloro‐5,6‐dicyanobenzoquinone (DDQ) and Sc(OTf)₃. Beside the red‐shifted absorption spectrum and split first oxidation potential that are common to the triply‐linked Zn^II–diporphyrins, diporphyrin 3 exhibited considerably improved chemical stability owing to a lowered HOMO and good solubility in common organic solvents. The two‐photon absorption (TPA) cross‐section and S₁‐state lifetime of compound 3 were 1700 GM and 3.3 ps, respectively.     

Synthesis of a Benzenethiol‐derivatized Porphyrin for Self‐assembly

The synthesis of a benzenethiol‐derivatized porphyrin for flat‐lying self‐assembly on gold substrates is described. Acetyl protected thiol is not stable enough in Pd‐catalyzed reactions. While acrylate derivatives protected thiol group shows good tolerance in Pd‐catalyzed borylations and Suzuki‐Miyaura coupling reactions and no catalyst poisoning was observed.     

Fabrication of Microspheres from Phthalimide‐Substituted Porphyrin Derivatives

Microspheres were fabricated from phthalimide‐substituted porphyrin derivatives. Microscopic analysis showed that the structures of the supramolecular assemblies synthesized in the present study were spherical, with diameters in the sub‐micrometer to micrometer range. The size of the microspheres could be controlled by changing the concentration of the casting solution. The spectroscopic properties of the microspheres were measured to determine the influence of their structural components. Thermal studies indicated that the temperature at which these structures became unstable was lower than the bulk melting point. During I–V measurements on devices composed of these microspheres, it was found that the current increased upon light irradiation, and the characteristic photoresponse properties of these devices were reproducible.     

A Waterwheel‐Shaped meso–meso‐Linked Porphyrin Pentamer

Wheels on water? A waterwheel‐shaped porphyrin pentamer has been synthesized by palladium‐catalyzed cross‐coupling reactions. The key intermediate is a boronate porphyrin, in which four boronic ester groups are directly attached to the meso‐positions.

     

Nucleophilic Substitution on Porphyrin Ring： Synthesis of 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenylporphyrin

The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.     

Peptide‐Induced Hierarchical Long‐Range Order and Photocatalytic Activity of Porphyrin Assemblies

Long‐range structural order and alignment over different scales are of key importance for the regulation of structure and functionality in biology. However, it remains a great challenge to engineer and assemble such complex functional synthetic systems with order over different length scales from simple biologically relevant molecules, such as peptides and porphyrins. Herein we describe the successful introduction of hierarchical long‐range order in dipeptide‐adjusted porphyrin self‐assembly by a thermodynamically driven self‐orienting assembly pathway associated with multiple weak interactions. The long‐range order and alignment of fiber bundles induced new properties, including anisotropic birefringence, a large Stokes shift, amplified chirality, and excellent photostability as well as sustainable photocatalytic activity. We also demonstrate that the aligned fiber bundles are able to induce the epitaxially oriented growth of Pt nanowires in a photocatalytic reaction.     

Halide Anion Mediated Dimerization of a meso‐Unsubstituted N‐Confused Porphyrin

The new N‐confused porphyrin (NCP) derivatives, meso‐unsubstituted β‐alkyl‐3‐oxo N‐confused porphyrin (3‐oxo‐NCP) and related macrocycles, were synthesized from appropriate pyrrolic precursors by a [3+1]‐type condensation reaction. 3‐Oxo‐NCP forms a self‐assembled dimer in dichloromethane that is stabilized by complementary hydrogen‐bonding interactions arising from the peripheral amide‐like moieties. The protonated form of 3‐oxo‐NCP was observed to bind halide anions (F^?, Cl^?) through the outer NH and the inner pyrrolic NH groups, thus affording a dimer in dichloromethane. The structure of the chloride‐bridged dimer in the solid state was determined by X‐ray diffraction analysis.     

Effects of Core‐modification on Porphyrin Sensitizers to the Efficiencies of Dye‐sensitized Solar Cells

To study dye‐sensitized solar cells (DSSCs) with core‐modified porphyrins as the sensitizing dyes, three porphyrins with an ethynyl benzoic acid as an anchoring group are prepared. The properties of free‐base regular porphyrin (N4), thiaporphyrin (N3S) and oxaporphyrin (N3O) were thoroughly studied by spectroscopic methods, DFT calculations, and photovoltaic measurements. Replacing one of the porphyrinic core nitrogen atoms by oxygen or sulfur considerably changes the absorption spectra. The Soret band of the N3O and N3S observed bathochromic shifts of 3‐9 nm while the Q band reaches 700 nm to the near‐infrared region. The overall conversion efficiencies of the DSSCs based on these porphyrins are in the order N4 (3.66%) ? N3S (0.22%) > N3O (0.01%). The time‐correlated single photon counting observed short fluorescence lifetimes for N3O adsorbed both on TiO₂ and Al₂O₃ which explicates the poor efficiency of DSSC using N3O as the photosensitizer.     

N‐Annulated Perylene‐Substituted and Fused Porphyrin Dimers with Intense Near‐Infrared One‐Photon and Two‐Photon Absorption

Fusion of two N‐annulated perylene (NP) units with a fused porphyrin dimer along the S₀–S₁ electronic transition moment axis has resulted in new near‐infrared (NIR) dyes 1 a / 1 b with very intense absorption (ε>1.3×10⁵ M ^?1 cm^?1) beyond 1250 nm. Both compounds displayed moderate NIR fluorescence with fluorescence quantum yields of 4.4×10^?6 and 6.0×10^?6 for 1 a and 1 b , respectively. The NP‐substituted porphyrin dimers 2 a / 2 b have also been obtained by controlled oxidative coupling and cyclodehydrogenation, and they showed superimposed absorptions of the fused porphyrin dimer and the NP chromophore. The excited‐state dynamics of all of these compounds have been studied by femtosecond transient absorption measurements, which revealed porphyrin dimer‐like behaviour. These new chromophores also exhibited good nonlinear optical susceptibility with large two‐photon absorption cross‐sections in the NIR region due to extended π‐conjugation. Time‐dependent density functional theory calculations have been performed to aid our understanding of their electronic structures and absorption spectra.     

A 1,3‐Phenylene‐Bridged Hexameric Porphyrin Wheel and Efficient Excitation Energy Transfer along the Wheel

A 1,3‐phenylene‐bridged hexameric Zn^II porphyrin wheel was synthesized by a Suzuki–Miyaura coupling reaction through a one‐pot or a stepwise route. The hexameric wheel structure was revealed by using X‐ray diffraction analysis. The porphyrin wheel exhibits a split Soret band due to effective exciton coupling and displays efficient excitation energy transfer along the wheel. Measurements of fluorescence anisotropy decay and pump‐power‐dependent decay reveal a rapid excitation energy hopping along the wheel with a rate of 1.4 ps.     

Cyclodextrin‐Templated Porphyrin Nanorings

α‐ and β‐Cyclodextrins have been used as scaffolds for the synthesis of six‐ and seven‐legged templates by functionalizing every primary CH₂OH with a 4‐pyridyl moiety. Although these templates are flexible, they are very effective for directing the synthesis of macrocyclic porphyrin oligomers consisting of six or seven porphyrin units. The transfer of chirality from the cyclodextrin templates to their nanoring hosts is evident from NMR and circular dichroism spectroscopy. Surprisingly, the mean effective molarity for binding the flexible α‐cyclodextrin‐based template within the six‐porphyrin nanoring (74 M ) is almost as high as for the previously studied rigid hexadentate template (180 M ). The discovery that flexible templates are effective in this system, and the availability of a template with a prime number of binding sites, open up many possibilities for the template‐directed synthesis of larger macrocycles.     

Nonlinear Optical Properties of Porphyrin Derivatives with Electron‐donating or Electron‐withdrawing Substituents

To investigate photoelectric properties of meso‐extended porphyrin derivatives with electron‐donating or electron‐withdrawing substituents, a series of functionalized porphyrin materials have been designed and synthesized by Suzuki coupling reaction. The meso‐extended structures were fully characterized by ¹H NMR, IR spectroscopy and mass spectrometry. The photophysical properties of porphyrin derivatives were carefully examined by UV‐Visible and fluorescence spectra, and the solvatochromic effect was observed and discussed. In particular, Z‐scan technique was employed to characterize the third‐order nonlinear optical (NLO) properties of the products such as nonlinear absorption and refraction, the third‐order nonlinear refractive indexes (??⁽³⁾‐value) of these porphyrin derivatives achieved 3.9×10^?12 esu. In addition, the compounds could be self‐assembled into highly organized morphologies through phase‐exchange method. All the results indicated that the discotic materials have the potential for optoelectronic applications.