Various aromatic segments have been fused onto the porphyrin periphery to create porphyrinoids that expanded π-conjugated networks and thus exhibit red-shifted absorption spectra. Fused coplanar oligomers, represented by meso–meso, β–β, β–β triply linked arrays (porphyrin tapes), are endued with more spectra better nonlinear optical properties. These emerged as promising near-infrared (NIR) absorbing dyes, pointing future applications such conducting wire, NIR emitter, photovoltaics,...

Abstract After a brief survey of our efforts in the development novel porphyrinoids that include meso–meso-linked porphyrin arrays, meso-aryl expanded porphyrins, and transition-metal-catalyzed functionalizations particular focus this account is placed on chemistry subporphyrins has been explored group. Subporphyrin legitimate ring-contracted consisting three pyrrolic subunits domed C3 symmetric bowl shape. While are simple small macrocycles possess key position chemistry, they had elusive...

β-to-β Directly linked cyclic Ni(II) porphyrin trimer, tetramer, and pentamer ([3]CP, [4]CP, [5]CP) have been synthesized by reaction of a 2,12-diborylated with Pt(cod)Cl2 followed reductive elimination. The structures these arrays revealed X-ray diffraction analysis. strain energies oligomers are calculated to be 77, 57, 47 kcal/mol for [3]CP, [5]CP, respectively. Intramolecular excitation energy hopping was observed between the 3(d,d) states porphyrins rates 3.0, 4.4, 4.6 ps respectively,...

Tetrabenzotetraaza[8]circulene (1) has been synthesized in good yield by a "fold-in" oxidative fusion reaction of 1,2-phenylene-bridged cyclic tetrapyrrole. X-ray diffraction analysis 1 revealed planar square structure with central cyclooctatetraene (COT) core that shows little alternation the bond lengths. Despite these structural features, aromatic-like character, such as sharp absorption bands, high fluorescence quantum yields (Φ(F)=0.55 THF), and single exponential decay τ(F)=3.8 ns....

A series of dihetero[8]helicenes have been systematically synthesized in enantiomerically enriched forms by utilizing the characteristic transformations organosulfur functionality. The synthetic route begins with assembling a ternaphthyl common intermediate from 2-naphthol and bissulfinylnaphthalene through an extended Pummerer reaction followed facile multi-gram-scale resolution. subsequent cyclization reactions into dioxa- dithia[8]helicenes take place excellent axial-to-helical chirality...

Synthetic challenges toward anomalous structures and electronic states often involve handling problems such as insolubility in common organic solvents oxidative degradation under aerobic conditions. We designed benzo-annulated aza[n]helicenes, which benefit from both the suppressed elevation of highest occupied molecular orbital (HOMO) energies high solubility due to hydrogen bonding with solvent molecules overcome these challenges. This strategy enabled synthesis six new aza[n]helicenes...

The entire phonon-dispersion curves along the $\overline{\ensuremath{\Gamma}}\mathrm{\text{\ensuremath{-}}}\overline{\mathrm{M}}$ direction of a ${\mathrm{B}\mathrm{C}}_{3}$ honeycomb sheet have been determined both experimentally and theoretically for first time. Most observed agreed with theoretical ones calculated on basis ab initio theory. From stretching force constants nearest-neighbor C-C B-C bonds, together that B-B bond, we clarified characteristic feature bonds. experimental...

Synthesis of stable open-shell polyradicaloids including control intramolecular spin–spin interactions is a challenging topic in organic chemistry and materials science. Herein, we report the synthesis physical characterization two series fluorenyl based macrocyclic polyradicaloids. In one (FR-MCn, n = 4–6), radicals are directly linked at 3,6-positions; whereas other (MC-FnAn, 3–5), an additional ethynylene moiety inserted between neighboring units. To access polyradicaloids, three...

We describe the synthesis and characterization of directly meso-meso linked porphyrin-[26]hexaphyrin-porphyrin hybrid oligomers their triply (completely fused) tapes. Linked Ni(II) porphyrin-[26]hexaphyrin-Ni(II) porphyrin trimers were prepared by methanesulfonic acid-catalyzed cross-condensation meso-formyl porphyrins with a 5,10-diaryltripyrrane followed oxidation 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The moieties converted to Zn(II) via an indirect route involving reduction...

Laterally extended zethrenes can be regarded as Z-shaped nanographenes with four zigzag edges, but their synthesis is very challenging. Herein, we report the successful of by far largest zethrene molecule, a superoctazethrene (SOZ) derivative SOZ-Cl, in crystalline form. Although parent SOZ calculated to have large diradical character ( y0 = 81.0%), SOZ-Cl shows reasonable stability t1/2 64 h under ambient conditions) and purified silica gel column chromatography. It exhibits small...

Abstract We report the synthesis and characterization of L‐ T‐shaped porphyrin tapes as extensible structural motifs two‐dimensionally extended tapes. The two‐photon absorption (TPA) cross‐section values ( σ (2) ) for well those linear trimeric tetrameric were measured by an open‐aperture Z‐scan method at 2300 nm, a wavelength which one‐photon contribution is either zero or almost negligible. Under these conditions, tape trimer tetramer determined to be 18 500 41 200 GM, respectively. value...

Twist and sort out! Chiral separation of PdII, NiII, PtII complexes [28]hexaphyrin(1.1.1.1.1.1) was achieved by HPLC on a chiral stationary phase (see inset for CD trace). The absolute configuration the PdII complex determined X-ray crystallography. Asymmetric metalation hexaphyrin, with binap salt, resulted in 23 % ee. This is first example asymmetric synthesis Möbius-twisted molecules. Detailed facts importance to specialist readers are published as ”Supporting Information”. Such documents...

Hybrid porphyrin tapes 3 and 4, consisting of a mixture 3,5-di-tert-butylphenyl-substituted donor-type Zn(II)-porphyrins pentafluorophenyl-substituted acceptor-type Zn(II)-porphyrins, were prepared by synthetic route involving cross-condensation reaction Ni(II)-porphyrinyldipyrromethane pentafluorophenyldipyrromethane with pentafluorobenzaldehyde followed appropriate demetalation, remetalation, oxidative ring-closure reaction. The Ni(II)-substituted 5 (Ni-Zn-Ni) 6 (Ni-H(2)-Ni) also through...

A meso-meso linked porphyrin–hexaphyrin hybrid was synthesized by the cross condensation using meso-porphyrinyl-dipyrromethane and oxidized with DDQ-Sc(OTf)3 to afford a porphyrin–[26]hexaphyrin tape that reduced NaBH4 give porphyrin–[28]hexaphyrin tape. Fully electronic conjugations in tapes are observed UV/vis/NIR absorption spectra, electrochemistry, excited-state dynamics.

FeCl3-mediated oxidative fusion of meso-linked dibenzo[a,g]corannulene–porphyrin dyads 6M afforded fused porphyrins 7M bearing a five-membered ring connection, but similar oxidation β-linked 9M provided 10M six-membered both in regiospecific manner. While exhibit modestly red-shifted absorption and fluorescence profiles, display characteristically bands reflecting antiaromatic dehydropurpurin electronic networks.

All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF2-complex 3 smoothly by 2-fold SNAr reaction of 1,9-dibromo-5-mesityldipyrrin with 5,10-dimesityltripyrrane. Treatment methanesulfonic acid gave [20]smaragdyrin 5 as stable antiaromatic compound. Reduction NaBH4 under inert conditions [22]smaragdyrin 6 an aromatic congener, which easily oxidized back to in air. Complex interconvertible its...

Abstract The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl 3 afforded meso–meso, β–β, β–β triply 2 H ‐corrole (with two inner NH groups each unit), which exhibited characteristic 1 NMR and absorption spectra attributable to their nonaromatic electronic networks. These were reduced NaBH 4 aromatic dimers, unstable easily oxidized back the upon exposure air. Bis(zinc(II)) complexes synthesized characterized as rare examples zinc(II) complexes.

Abstract Oxidative fusion reactions of ortho ‐phenylene‐bridged cyclic hexapyrroles and hexathiophenes furnished novel closed helicenes in a selective manner. X‐Ray diffraction analysis unambiguously revealed the structures to be pentaaza[9]helicene, longest azahelicene reported so far, an unexpected double‐helical structure hexathia[9]/[5]helicene, whose formation was assumed result from multiple oxidative along with 1,2‐aryl shift. The pentaaza[9]helicene exhibited well‐defined emission...

A singly linked corrole dimer was synthesized by condensation of a dipyrromethane-1-carbinol with 1,1,2,2-tetrapyrroethane. Oxidation the gave doubly dimers 9 and 10 as first examples fused involving meso-meso linkage. Dimers exhibit characteristic (1)H NMR spectra, absorption excited-state dynamics, two-photon (TPA) values, which indicate nonaromatic nature aromatic 10. Interestingly, is fairly stable despite its unusual 2H-corrole structure, has been ascribed to presence two direct...

Abstract A reaction sequence of regioselective peripheral bromination, Suzuki–Miyaura coupling with 2‐borylated thiophene or pyrrole, and oxidative ring‐closure FeCl 3 allowed the synthesis heterole‐fused earring porphyrins 4Pd 9Pd from parent porphyrin 1 . Differently pyrrole‐fused 5H 6H their Pd II complexes 5Pd 6Pd were also synthesized. The structures , 5H, 8Pd have been revealed by X‐ray analysis to be slightly twisted owing constraints imposed structures. exhibits an intensified band...