Porphyrin nanotubes based on a hydrogen-bonded organic framework.

Tubular structures offer a wide variety of applications; therefore, designing such materials with distinct dimensions is highly desirable yet challenging. In the current report, we have demonstrated the synthesis of a one-dimensional (1D) tubular assembly comprising porphyrin nanoring subunits. The porphyrin nanoring (PNR) 2 bearing ester groups was synthesized via Pt-mediated cyclization and then hydrolyzed to obtain PNR 3 with carboxylic groups. Under optimized conditions, porphyrin nanotubes (PNTs) were formed through hydrogen bonding between the carboxylic groups of 3. The morphology investigated by both SEM and TEM displayed well-defined arrays of nanotube bundles up to several micrometers long. Small crystals of PNTs were obtained by heating a solution of 3 in DMSO. High-resolution transmission electron microscopy (HR-TEM) accompanied by selected-area electron diffraction (SAED) exhibited a line of diffractions with d-spacing values of 6.17, 3.08, 2.07, and 1.57 Å. The miller indices of these diffractions could be assigned as 300, 600, 900, and 1200, respectively, suggesting that an ordered structure of 1D PNTs has been formed.

Porphyriynes: 18-π-Conjugated Macrocycles Incorporating a Triple Bond.

Tetraphenylporphyriyne (Pyne1), a novel porphyrin analogue with a C≡C bond incorporated into an 18-π-conjugated system, has been created via cleavage of the N-confused pyrrolic ring in Ag(III) N-confused tetraphenylporphyrin. The structure of Pyne1 was confirmed by X-ray crystallography and 1H NMR, IR, and UV-vis spectroscopy. The mechanism of cleavage of the N-confused pyrrolic ring was investigated by theoretical calculations. The successful synthesis of other Pynes indicated the generality of this protocol.

Formation of Stable NiIII N-Confused Porphyrins Aided by a 3-Ethoxy Group.

We report the synthesis, characterization, and reactivities of two stable NiIII N-confused porphyrin (NCP) complexes. Metalation of 3-OEt NCP 1 with NiCl2 ⋅ 6H2 O in CHCl3 /EtOH gave 3-OEt NiII NCP 3 initially, which was easily oxidized in air to form the NiIII complex of NCP inner C-oxide 4. Bis-ethoxy-modified NiIII complex 5 was synthesized by oxidation of 3 with PIFA in ethanol and CHCl3 . The structures of 4 and 5 were determined by single-crystal X-ray diffraction analysis. An unusually long NiIII -C bond (2.170(9) Å) was observed in 4. The g-factor (g>2.1) observed in the EPR spectra of 4 and 5 further confirmed that they are paramagnetic NiIII complexes. Comparative experiments showed that the 3-ethoxy group plays an important role in the formation of 4 and 5. Reduction of 4 and 5 with NaBH4 regenerated complex 3.

Global aromaticity at the nanoscale.

Aromaticity can be defined by the ability of a molecule to sustain a ring current when placed in a magnetic field. Hückel's rule states that molecular rings with [4n + 2] π-electrons are aromatic, with an induced magnetization that opposes the external field inside the ring, whereas those with 4n π-electrons are antiaromatic, with the opposite magnetization. This rule reliably predicts the behaviour of small molecules, typically with fewer than 22 π-electrons (n = 5). It is not clear whether aromaticity has a size limit, or whether Hückel's rule extends to much larger macrocycles. Here, we present evidence for global aromaticity in porphyrin nanorings with circuits of up to 162 π-electrons (n = 40); aromaticity is controlled by changing the constitution, oxidation state and conformation. Whenever a ring current is observed, its direction is correctly predicted by Hückel's rule. The largest ring currents occur when the porphyrin units have fractional oxidation states.

Cross-conjugation increases the conductance of meta-connected fluorenones.

Charge transport is strongly suppressed by destructive quantum interference (DQI) in meta-connected 1,1'-biphenyl-containing molecules, resulting in low electrical conductance. Surprisingly, we have found that DQI is almost entirely overcome by adding a bridging carbonyl, to yield a cross-conjugated fluorenone. This contrasts with other π-systems, such as para-connected anthraquinone, where cross-conjugation results in low conductance.

Chidamide, a histone deacetylase inhibitor, induces growth arrest and apoptosis in multiple myeloma cells in a caspase-dependent manner.

Chidamide, a novel histone deacetylase (HDAC) inhibitor, induces antitumor effects in various types of cancer. The present study aimed to evaluate the cytotoxic effect of chidamide on multiple myeloma and the underlying mechanisms involved. Viability of multiple myeloma cells upon chidamide treatment was determined by the Cell Counting Kit-8 assay. Apoptosis induction and cell cycle alteration were detected by flow cytometry. Specific apoptosis-associated proteins and cell cycle proteins were evaluated by western blot analysis. Chidamide suppressed cell viability in a time- and dose-dependent manner. Chidamide treatment markedly suppressed the expression of type I HDACs and further induced the acetylation of histones H3 and H4. In addition, it promoted G0/G1 arrest by decreasing cyclin D1 and c-myc expression, and increasing phosphorylated-cellular tumor antigen p53 and cyclin-dependent kinase inhibitor 1 (p21) expression in a dose-dependent manner. Treatment with chidamide induced cell apoptosis by upregulating the apoptosis regulator Bax/B-cell lymphoma 2 ratio in a caspase-dependent manner. In addition, the combination of chidamide with bortezomib, a proteasome inhibitor widely used as a therapeutic agent for multiple myeloma, resulted in enhanced inhibition of cell viability. In conclusion, chidamide induces a marked antimyeloma effect by inducing G0/G1 arrest and apoptosis via a caspase-dependent pathway. The present study provides evidence for the clinical application of chidamide in multiple myeloma.

Tuning the Circumference of Six-Porphyrin Nanorings.

Most macrocycles are made from a simple repeat unit, resulting in high symmetry. Breaking this symmetry allows fine-tuning of the circumference, providing better control of the host-guest behavior and electronic structure. Here, we present the template-directed synthesis of two unsymmetrical cyclic porphyrin hexamers with both ethyne (C2) and butadiyne (C4) links, and we compare these nanorings with the symmetrical analogues with six ethyne or six butadiyne links. Inserting two extra carbon atoms into the smaller nanoring causes a spectacular change in binding behavior: the template affinity increases by a factor of 3 × 109, to a value of ca. 1038 M-1, and the mean effective molarity is ca. 830 M. In contrast, removing two carbon atoms from the largest nanoring results in almost no change in its template-affinity. The strain in these nanorings is 90-130 kJ mol-1, as estimated both from DFT calculation of homodesmotic reactions and from comparing template affinities of linear and cyclic oligomers. Breaking the symmetry has little effect on the absorption and fluorescence behavior of the nanorings: the low radiative rates that are characteristic of a circular delocalized S1 excited state are preserved in the low-symmetry macrocycles.

Detecting Mechanochemical Atropisomerization within an STM Break Junction.

We have employed the scanning tunneling microscope break-junction technique to investigate the single-molecule conductance of a family of 5,15-diaryl porphyrins bearing thioacetyl (SAc) or methylsulfide (SMe) binding groups at the ortho position of the phenyl rings (S2 compounds). These ortho substituents lead to two atropisomers, cis and trans, for each compound, which do not interconvert in solution under ambient conditions; even at high temperatures, isomerization takes several hours (half-life 15 h at 140 °C for SAc in C2Cl4D2). All the S2 compounds exhibit two conductance groups, and comparison with a monothiolated (S1) compound shows the higher group arises from a direct Au-porphyrin interaction. The lower conductance group is associated with the S-to-S pathway. When the binding group is SMe, the difference in junction length distribution reflects the difference in S-S distance (0.3 nm) between the two isomers. In the case of SAc, there are no significant differences between the plateau length distributions of the two isomers, and both show maximal stretching distances well exceeding their calculated junction lengths. Contact deformation accounts for part of the extra length, but the results indicate that cis-to-trans conversion takes place in the junction for the cis isomer. The barrier to atropisomerization is lower than the strength of the thiolate Au-S and Au-Au bonds, but higher than that of the Au-SMe bond, which explains why the strain in the junction only induces isomerization in the SAc compound.

A meso-meso ß-ß ß-ß Triply Linked Subporphyrin Dimer.

A meso-meso ß-ß ß-ß triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of ß-to-ß doubly PtII -bridged subporphyrin dimer 9. Dimer 6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time-resolved transient absorption spectroscopy. X-ray diffraction analysis reveals that 6 has a bowl-shaped structure with a positive Gaussian curvature. Despite the curved structure, 6 exhibits a remarkably red-shifted absorption band at 942 nm and a small electrochemical HOMO-LUMO gap (1.35 eV), indicating an effectively conjugated π-electronic network.

Unexpected Interactions between Alkyl Straps and Pyridine Ligands in Sulfur-Strapped Porphyrin Nanorings.

Strapped or "basket-handle" porphyrins have been investigated previously as hemoglobin mimics and catalysts. The facial selectivity of their interactions with axial ligands is a sensitive test for noncovalent bonding. Here the binding of pyridyl ligands to zinc porphyrins with thioester-linked alkyl straps is investigated in solution by NMR spectroscopy and UV-vis titration, and in the solid state by X-ray crystallography. We expected that coordination of the axial ligand would occur on the less hindered face of the porphyrin, away from the strap. Surprisingly, attractive interactions between the strap and the ligand direct axial coordination to the strapped face of the porphyrin, except when the strap is short and tight. The strapped porphyrins were incorporated into π-conjugated cyclic porphyrin hexamers using template-directed synthesis. The strap and the sulfur substituents are located either inside or outside the porphyrin nanoring, depending on the length of the strap. Six-porphyrin nanorings with outwardly pointing sulfur anchors were prepared for exploring quantum interference effects in single-molecule charge transport.

Exciton coupling dynamics in syn- and anti-type ß-ß linked Zn(ii) porphyrin linear arrays.

The photophysical properties of molecular arrays are strongly dependent on a variety of structural factors: the constituent chromophores, dihedral angle, linkage length, linkage position, the center-to-center distance between chromophores, and the linker itself. Here, we investigated the exciton coupling dynamics of syn- and anti-type ß-ß directly linked Zn(ii) porphyrin linear arrays. Focusing on the relationship between the origin of the lowest excited electronic state and the linkage position, we evaluated the exciton coupling strength and carried out time-dependent density functional theory (TDDFT) calculations on model compounds as well as femtosecond transient absorption anisotropy (fs-TAA) measurements. Based on our experiments and calculations, we propose that a different origin of the lowest excited state leads to linkage-position-dependent exciton coupling. In short, compared with syn-type porphyrin arrays, anti-type arrays induce distinct and stronger exciton coupling in the lowest excited state.

Directly 2,12- and 2,8-Linked Zn(II) Porphyrin Oligomers: Synthesis, Optical Properties, and Coherence Lengths.

Directly 2,12- and 2,8-linked Zn(II) porphyrin oligomers were prepared from 2,12- and 2,8-diborylated Zn(II) porphyrin by a cross platinum-induced coupling with a 2-borylated Zn(II) porphyrin end unit followed by a triphenylphosphine (PPh3 )-mediated reductive elimination. Comparative studies on the steady-state absorption and fluorescence spectra and the fluorescence lifetimes led to a conclusion that the exciton in the S1 state is delocalized over approximately four and two Zn(II) porphyrin units for 2,12- and 2,8-linked Zn(II) porphyrin arrays, respectively.

Synthesis of [n]Cyclo-5,15-porphyrinylene-4,4'-biphenylenes Displaying Size-Dependent Excitation-Energy Hopping.

A set of 5,15-biphenylene-bridged porphyrin wheels, namely, [n]cyclo-5,15-porphyrinylene-4,4'-biphenylenes [n]CPB, have been synthesized through the platination of 5,15-bis(4-(pinacolboranyl)phenyl) nickel(II) porphyrin and subsequent reductive elimination of Pt(II) (cod)-bridged cyclic porphyrin intermediates. The calculated strain energies for [3]CPB, [4]CPB, [5]CPB, and [6]CPB are 49.3, 32.9, 23.5, and 16.0 kcal mol(-1) , respectively. UV/Vis absorption spectra and cyclic voltammetry indicated characteristic ring-size-dependent absorption-peak shifts and redox-potential shifts, which presumably reflect the degree of strain in the π-systems. Excitation-energy hopping (EEH) times were determined to be 5.1, 8.0, 8.0, and 9.6 ps for [3]CPB, [4]CPB, [5]CPB, and [6]CPB, respectively, in a pump-power-dependent TA experiment.

Cyclic 2,12-porphyrinylene nanorings as a porphyrin analogue of cycloparaphenylenes.

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

Singly and doubly ß-to-ß platinum-bridged porphyrin dimers and their reductive eliminations.

2-Borylated porphyrins reacted with Pt(cod)Cl2 to give ß-to-ß platinum-bridged porphyrin dimers, which were converted to ß-to-ß directly linked porphyrin dimers through triphenylphosphine-mediated reductive elimination. Similar reactions of 2,18-diborylated Ni(ii)-porphyrin and Zn(ii)-porphyrin gave the corresponding doubly ß-to-ß platinum-bridged porphyrin dimers. Treatment of the doubly ß-to-ß platinum-bridged Ni(ii)-porphyrin dimer with triphenylphosphine caused a single reductive elimination to produce a Ni(ii)-porphyrin dimer possessing a ß-to-ß platinum bridge and a ß-to-ß direct C-C bond.

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.

Electrophilic fluoroalkylation of Ni(II) N-confused porphyrins with fluoroalkylarylsulfonium salts.

Experimental studies showed that Ni(II) N-confused porphyrins, treated with fluoroalkylarylsulfonium salts, can undergo an electrophilic fluoroalkylation at the inner 21-C position, leading to 21-fluoroalkylated Ni(II) N-confused porphyrins.

Electrophilic reaction of Ag(III) N-confused porphyrin with alcohols.

Experimental studies demonstrated that alcohols and amines can undergo a CF(3)COOAg-catalyzed nucleophilic addition at the outer C=N position of Ag(III) NCPs, leading to C-3-alkoxylated Ag(III) NCPs, which supports the computational result that the C=N bond on the periphery of Ag(III) NCPs is partially isolated from the 18 pi-electron macrocyclic conjugation system and is the active electrophilic center.

The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators and an unexpected intramolecular nucleophilic substitution reaction via a proposed Ni(III) NCP intermediate.

The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators resulted in an unexpected intramolecular nucleophilic substitution reaction via a proposed Ni(III) NCP intermediate, which could be detected by HRMS.

Synthesis and reactions of the first fluoroalkylated Ni(II) N-confused porphyrins.

The first fluoroalkylated Ni(ii) N-confused porphyrins were synthesized with high regioselectivity and its further alkylation was studied.