Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach

Oxidative polymerization of nickel(II) 5,15‐diphenyl porphyrin and nickel(II) 5,15‐bis(di‐3,5‐tert‐butylphenyl) porphyrin by oxidative chemical vapor deposition (oCVD) yields multiply fused porphyrin oligomers in thin film form. The oCVD technique enables one‐step formation, deposition, and p‐doping of conjugated poly(porphyrins) coatings without solvents or post‐treatments. The decisive reactions and side reactions during the oCVD process are shown by high‐resolution mass spectrometry. Owing to the highly conjugated structure of the fused tapes, the thin films exhibit an electrical conductivity of 3.6×10^?2 S cm^?1 and strong absorption in the visible to near‐infrared spectral region. The formation of smooth conjugated poly(porphyrins) coatings, even on sensitive substrates, is demonstrated by deposition and patterning on glass, silicon, and paper. Formation of conductive poly(porphyrins) thin films could enable the design of new optoelectronic devices using the oCVD approach.     

Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.     

Fusing Porphyrins and Phospholes: Synthesis and Analysis of a Phosphorus‐Containing Porphyrin

A phosphole‐fused porphyrin dimer, as a representative of a new class of porphyrins with a phosphorus atom, was synthesized for the first time. The porphyrin dimer exhibits remarkably broadened absorption, indicating effective π‐conjugation over the two porphyrins through the phosphole moiety. The porphyrin dimer possesses excellent electron‐accepting character, which is comparable to that of a representative electron‐accepting material, [60]PCBM. These results provide access to a new class of phosphorus‐containing porphyrins with unique optoelectronic properties.     

Opp‐Dibenzoporphyrins as a Light‐Harvester for Dye‐Sensitized Solar Cells

New opp‐dibenzoporphyrins were prepared in a concise method that was based on a Pd⁰‐catalyzed cascade reaction. These porphyrins, which contained carboxylic‐acid linker groups on benzene rings that were fused to the porphyrin at their β,β′‐positions, were examined as sensitizers for dye‐sensitized solar cells for the first time. Whereas all of the porphyrins showed solar‐energy‐to‐electricity conversion, an opp‐dibenzoporphyrin with conjugated carboxylic‐acid linkers displayed the highest conversion efficiency and an exceptionally high J_sc value. Cyclic voltammetry of these porphyrins suggested that the fusion of two aromatic benzene rings onto the periphery of the porphyrin lowered the HOMO–LUMO energy gap; the incorporation of a conjugated carboxylic‐acid linker group decreased the HOMO–LUMO gap even further. These CV data are consistent with DFT calculations for these porphyrins and agree well with the UV/Vis absorption‐ and fluorescence spectra of these porphyrins.     

Synthesis of Triply Fused Porphyrin‐Nanographene Conjugates

Two unprecedented porphyrin fused nanographene molecules, 1 and 2 , have been synthesized by the Scholl reaction from tailor‐made precursors based on benzo[m]tetraphene‐substituted porphyrins. The chemical structures were validated by a combination of high‐resolution matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (HR MALDI‐TOF MS), IR and Raman spectroscopy, and scanning tunnelling microscopy (STM). The UV‐vis‐near infrared absorption spectroscopy of 1 and 2 demonstrated broad and largely red‐shifted absorption spectra extending up to 1000 and 1400 nm, respectively, marking the significant extension of the π‐conjugated systems.     

Heteroleptic Tetrapyrrole‐Fused Dimeric and Trimeric Skeletons with Unusual Non‐Frustrated Fluorescence

Phthalocyanine (Pc) and porphyrin (Por) chromophores have been fused through the benzo[α]pyrazine moiety, resulting in unprecedented heteroleptic tetrapyrrole‐fused dimers and trimers. The heteroleptic tetrapyrrole nature has been clearly revealed based on single‐crystal X‐ray diffraction analysis of the zinc dimer. Electrochemical analysis, theoretical calculations, and time‐resolved spectroscopic results disclose that the two/three‐tetrapyrrole‐fused skeletons behave as one totally π‐conjugated system as a result of the strong conjugative interaction between/among the tetrapyrrole chromophores. In particular, the effectively extended π‐electron system through the fused‐bridge induced strong electronic communication between the Pc and Por moieties and large transition dipole moments in the Pc–Por‐fused systems, providing high fluorescence quantum yields (>0.13) and relatively long excited state lifetimes (>1.3 ns) in comparison with their homo‐tetrapyrrole‐fused analogues.     

Nickel(II) Bisporphyrin-Fused Pentacenes Exhibiting Abnormal High Stability

A series of largely π-extended multichromophoric molecules including cross-conjugated, half cross-conjugated, conjugation-interrupted and linearly conjugated systems were synthesized and characterized. These multichromophoric molecular systems revealed interesting structural-property relationships. Bisporphyrin-fused pentacenes Pen-1 b and Pen-2 a showed rich redox chemistry with 7 and 8 observable redox states, respectively. The linearly-conjugated bisporphyrin-fused pentacenes ( Pen-1 b and Pen-2 a ) possess much narrower HOMO–LUMO gaps (1.65 and 1.42 eV redox, respectively) and higher HOMO energy levels than those of their pentacene analogues (2.23 and 2.01 eV redox, respectively), similar to those of much less stable hexacenes and heptacenes. An estimated half-life of >945 h was obtained for bisporphyrin-fused pentacene Pen-2 a , which is much longer than that of its pentacene analogue ( BPE-P , half-life, 33 h).     

meso‐3,5‐Bis(trifluoromethyl)phenyl‐Substituted Expanded Porphyrins: Synthesis,Characterization, and Optical,Electrochemical, and Photophysical Properties

Trifluoroacetic acid‐catalyzed condensation of pyrrole with electron‐deficient and sterically hindered 3,5‐bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso‐3,5‐bis(trifluoromethyl)phenyl‐substituted expanded porphyrins including [22]sapphyrin 2 , N‐fused [22]pentaphyrin 3 , [26]hexaphyrin 4 , and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20‐tetrakis(3,5‐bis(trifluoromethyl)phenyl)porphyrin 1 . These expanded porphyrins are characterized by mass spectrometry, ¹H NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO–LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced.     

Electronic structures and spectra of porphyrin with fused benzoheterocycles: DFT and TDDFT‐PCM investigations

Density functional theory (DFT) and time‐dependent DFT (TDDFT) are applied to study seven asymmetric π‐conjugated porphyrins with extended benzoheterocycles: quinoline, indole, benzoimidazole, benzothiazole, benzooxazole, 2,1,3‐benzothiadiazole, and 2,1,3‐benzoxadiazole. The solvation effects on the excitation energies for these porphyrin derivatives in chloroform are taken into account by using the continuum model (C‐PCM) combined with TDDFT, and this method makes a closer agreement with the experimental values, especially for the B‐bands of these objects. Great efforts have been made on investigating the influences of the fused aromatic units of the porphyrins on the absorption properties as these can be particularly important for many applications. Benzoheterocycle introduction and solvent effects have been systemically investigated, and close agreement is obtained between calculated and measured UV–vis spectra. These theoretical data could shed light on future synthetic chemistry. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Ruthenocene‐Type Complexes of N‐Fused Porphyrins

Ruthenocene‐type hybrid complexes with N‐fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N‐fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X‐ray crystallography. [Ru(NFp)Cp] is a common low‐spin ruthenium(II) complex and shows strong aromaticity. The Ru–Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp₂] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three‐dimensional d–π conjugated system. The HOMO–LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N‐fused porphyrin, in which the HOMO–LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.     

meso,β‐Oligohaloporphyrins as Useful Synthetic Intermediates of Diphenylamine‐Fused Porphyrin and meso‐to‐meso β‐to‐β Doubly Butadiyne‐Bridged Diporphyrin

The chlorination of β‐halo or β,β‐dihaloporphyrins with 2‐chloro‐1,3‐bis(methoxycarbonyl)guanidine (Palau′Chlor) proceeded selectively at the neighboring unsubstituted meso position to afford meso,β‐dihalo or meso,β,β‐trihaloporphyrins. Such oligohaloporphyrins are useful platforms for constructing more‐elaborate porphyrin‐based extended π systems. For example, meso‐chloro‐β,β‐diiodoporphyrin participated in an efficient single‐step synthesis of a diphenylamine‐fused porphyrin. In addition, meso‐chloro‐β‐iodoporphyrin was transformed in stepwise fashion into an efficiently conjugated meso‐to‐meso,β‐to‐β doubly butadiyne‐linked porphyrin dimer, a system which was previously difficult to access without such haloporphyrin precursors.     

Triphenylsilane‐fused Porphyrins

A reaction sequence of 2‐(diphenylsilyl)phenylation by Negishi coupling and intramolecular sila‐Friedel–Crafts reaction has been explored for the synthesis of mono‐triphenylsilane‐fused porphyrins 5 M and 6 M (M= Ni, Zn) and bis‐triphenylsilane‐fused porphyrins 7 M and 8 Ni . A triply linked triphenylsilane‐fused Ni^II porphyrin, 13 Ni , was synthesized in a stepwise manner involving the above reaction sequence and a final Pd‐catalyzed C?H activating arylative cyclization. The silicon atom in 13 Ni takes a distorted planarized structure with an almost perpendicular Si‐phenyl group, causing an electronic effect due to effective σ*–π* interaction.     

Synthesis, Characterization, and Electrochemical Property of Nanometer Porphyrin Dimer

A nanometer porphyrin dimer was synthesized with fumaryl chloride as a bridge-linked reagent. The characterization was carried out with elemental analyses, ^1H NMR, UV-Vis, and IR spectrometries, and then the electrochemical properties of the porphyrins were studied. The authors found that there was moderate electronic communication between the two porphyrin rings in the nanometer porphyrin dimer.     

Directly linked porphyrin arrays

The Ag(I)-promoted oxidative meso-meso coupling reaction of 5,15-diaryl Zn(II)-porphyrin was serendipitously found in the course of our synthetic approaches towards photosynthetic reaction centers. Based on this reaction, a variety of directly linked and fused porphyrin arrays have been synthesized, including linear meso-meso-linked porphyrin arrays, windmill- and grid-shaped porphyrin arrays, meso-beta singly linked diporphyrins, beta-beta linked diporphyrins, meso-beta doubly linked (fused) diporphyrins and oligoporphyrins, meso-meso beta-beta doubly linked (fused) diporphyrins, and meso-meso beta-beta-beta-beta triply linked (fused) diporphyrins. The meso-meso coupling reaction of 5,15-diaryl Zn(II)-porphyrins is advantageous considering its high regioselectivity as well as its ease of extension to large porphyrin arrays as is demonstrated by the synthesis of a discrete meso-meso-linked 128-mer and poly(5,15-porphyrinylene). Finally, the oxidation of end-phenyl capped meso-meso-linked zinc porphyrins with DDQ-Sc(OTf)(3) gave pi-conjugated flat porphyrin tapes. To the best of our knowledge, the meso-meso linked 128-mer is the longest man-made discrete molecule, and the porphyrin tape 12-mer is the most extensively conjugated porphyrin array, as evinced by the lowest electronic band peak at 3500 cm(-1).     

Directly Diphenylborane‐Fused Porphyrins

Mono‐ and bis(diphenylborane)‐fused porphyrins were synthesized from the corresponding β‐(2‐trimethylsilylphenyl)‐substituted porphyrins through the sequence of Si–B exchange reaction, intramolecular bora‐Friedel–Crafts reaction, and ring‐closing Si–B exchange reaction. Effective electronic interactions of the empty p‐orbital of the boron atom with the porphyrin π‐circuit lead to red‐shifted absorption spectra and substantially decreased LUMO energy levels. Pyridine adds at the boron center to cause disruption of the electronic interaction of the boron atom with large association constants (1.9–17×10⁴ m ^?1) depending on the central metal at the porphyrin. The Zn^II complex behaved as a hetero‐dinuclear Lewis acid, exhibiting regioselective binding of pyridines at the boron or the zinc center.     

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.     

Axial coordination of pyridyl-containing pentacenes to porphyrins

A pair of pentacenes that are functionalized in the 6-position with either a 3- or 4-pyridyl group via a triazole linker have been used to form complexes with a tetra(aryl)ruthenium(II) porphyrin through axial coordination. The pentacene–porphyrin dyads 5 and 6 have been structurally characterized through a combination of spectroscopic techniques. UV–vis spectroscopy shows that the absorption profiles of the two chromophores, the porphyrin and the pentacene, are complementary, providing absorptions throughout the UV and visible regions. While the dyads are reasonably stable in the solid state under ambient conditions they are, unfortunately, only stable in solution for hours when exposed to light and air.     

Pictet–Spengler Synthesis of Quinoline‐Fused Porphyrins and Phenanthroline‐Fused Diporphyrins

Doubly and quadruply quinoline‐fused porphyrins were effectively synthesized through a reaction sequence consisting of Suzuki–Miyaura coupling of β‐borylated porphyrins with 2‐iodoaniline and subsequent Pictet–Spengler cyclization. These quinoline‐fused porphyrins display red‐shifted absorption bands and higher electron‐accepting abilities. This synthetic protocol also allowed the synthesis of phenanthroline‐fused porphyrin dimers, which bound either a Ni^II or Zn^II cation. The resultant metal complexes displayed further red shifted absorption spectra and molecular twists to effect an almost perpendicular arrangement of the two porphyrins.     

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.     

Highly conjugated multiporphyrins: synthesis, spectroscopic and electrochemical properties

A series of meso-to-meso ethynyl-bridged multiporphyrin arrays have been synthesized using Sonogoshira palladium-catalyzed cross-coupling reactions involving the appropriate ethynylporphyrin and iodoporphyrin precursors. The absorption spectra of these multiporphyrins show splitting of the Soret bands and significant red shifts of the Q bands as compared to the combination of the corresponding components. These conjugated multiporphyrins also show red shifts in their emission spectra as the pi-conjugation is expanded. In the electrochemical measurements, the porphyrins dimer 7 shows two 1 - e- oxidations at E(1/2) = +0.63 and +0.76 V for the first electron abstraction from the two porphyrin rings, indicating electronic communication between the two porphyrin units. The porphyrin trimer 4 exhibits the first and second 1 - e- oxidations at E(1/2) = +0.68 and +0.77 V, respectively, which correspond to the two outer porphyrins. The cyclic voltammogram of pentamer 5 shows two overlapping 1 - e- couples at E(1/2) = +0.56 and +0.66 V, and one 2 - e- couple at E(1/2) = +0.86 V, for the four outer porphyrin units. These results demonstrate that in the porphyrin trimer and pentamer the individual peripheral porphyrin units are electrochemically coupled via a central porphyrin core. The UV-Vis-NIR spectra of the oxidized species of these multiporphyrins exhibit a broad intervalence charge transfer (IVCT) band in the region from 1200 to 3000 nm. The present work shows that a central porphyrin unit appended with ethynyl bridges affords strong electronic interactions between the peripheral porphyrin rings over a distance of about 15 A.