Naphthalocyanine Derivatives Research Articles

Surface Polarity Regulation by Relieving Fermi‐Level Pinning with Naphthalocyanine Tetraimides toward Efficient Perovskite Solar Cells with Improved Photostability

AbstractIn perovskite solar cells (PSCs), defective perovskite grain boundaries (GBs) and/or surface due to photo‐excitation and the resulted suboptimal carrier dynamics at the perovskite/charge transport layer, have largely limited further performance enhancement and aggravated the PSCs instability. Fundamentally preventing the formation of these trap‐states through a simple and efficient approach is thus critical to the enhancement of both device performance and stability. Herein, a novel semiconductive silicon naphthalocyanine derivative (Cl‐SiNcTI) to reduce the deep level trap states at the GBs and the surface of perovskite film is successfully employed via a newly proposed photon‐relaxation mechanism. The resulting benign p‐type surface polarity and suppressed non‐radiation recombination lead to improved charge transport in bulk perovskite and at the perovskite/spiro‐OMeTAD interface. With a synergistic contribution of the Cl‐SiNcTI and 2‐(2‐Fluorophenyl)ethylamine iodide (oFPEAI), a 24.30% efficiency is achieved in a single cell with excellent operational stability. Moreover, under steady‐state light illumination, 93% power output compared to its initial state can still be maintained after 250 h of continuous operation.

Solution-processable silicon naphthalocyanine tetraimides as near infrared electron acceptors in organic solar cells

Two silicon naphthalocyanine electron acceptors, CH3O-SiNcTI and 3BSO-SiNcTI, with four strong electron-withdrawing imide groups, were designed, synthesized, and applied in bulk heterojunction organic solar cells (BHJ OSCs). They exhibited strong near-infrared absorption in 300–1100 nm, maximum extinction coefficients of up to 5.2 × 105 M−1 cm−1, deep lowest unoccupied molecular orbital energy levels of −3.92 eV, and good photothermal stability. The power conversion efficiency of BHJ OSCs based on acceptor of 3BSO-SiNcTI reached 4.22%, which is the highest value among solution-processable phthalocyanine or naphthalocyanine derivatives. The measurements of space-charge-limited current, charge recombination, charge collection capability, atomic force microscopy (AFM), and transmission electron microscopy (TEM) were carried out. It is found that BHJ OSCs based on PTB7-Th:3BSO-SiNcTI, have higher and balanced carrier mobility, less charge recombination, better charge transport, and favorable film morphology, which lead to their higher photovoltaic performance. This study indicates the great potential of SiNcTIs as near-infrared chromophores for high-performance electron acceptors in BHJ OSCs.

Silicon Naphthalocyanine Tetraimides: Cathode Interlayer Materials for Highly Efficient Organic Solar Cells.

Naphthalocyanine derivatives (SiNcTI-N and SiNcTI-Br) were firstly used as excellent cathode interlayer materials (CIMs) in organic solar cells, via introducing four electron-withdrawing imide groups and two hydrophilic alkyls. Both of them showed deep LUMO energy levels (below -3.90 eV), good thermal stability (Td >210 °C), and strong self-doping property. The SiNcTI-Br CIM displayed high conductivity (4.5×10-5 S cm-1 ) and electron mobility (7.81×10-5 cm2 V-1 s-1 ), which could boost the efficiencies of the PM6:Y6-based OSCs over a wide range of CIM layer thicknesses (4-25 nm), with maximum efficiency of 16.71 %.

Unsymmetrical zinc (II) phthalocyanine and zinc (II) naphthalocyanine with 2,3-Dicyano-1,4-diphenylnaphthalene precursor

The synthesis, photophysical and photochemical properties of an unsymmetrical zinc (II) phthalocyanine and zinc (II) naphthalocyanine derivative are described. The precursor 2,3-Dicyano-1,4-diphenylnaphthalene was synthetized by Diels-Alder reaction with 1,3-diphenylisobenzofuran and fumaronitrile. The macrocycles were characterized by MALDI-TOF, FTIR, 1H NMR and UV–vis. On their spectroscopy, the impact of the added aromatic moiety was investigated in solution, observing a bathochromic shift in UV–vis absorption, emission and excitation spectra. The structural and electronic properties indicated that the geometry reorganization during the excitation and relaxation processes, and the dipole moment of the ground state, increases the generation of singlet oxygen in solution.

Photophysical and Photochemical Properties and Aggregation Behavior of Phthalocyanine and Naphthalocyanine Derivatives

The photophysical and photochemical properties of phthalocyanine and naphthalocyanine with similar structures were studied in solution and with density-functional theory (DFT) computational method. The extended π-conjugated system in naphthalocyanines causes a bathochromic shift in UV-Vis, emission and excitation bands, and promotes lesser generation of singlet oxygen in solution when compared to phthalocyanines. Time dependent DFT (TD-DFT) calculations point out the molecular orbitals involved in Q-band transition, corresponding to highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition with a concentration of charge along x-axis, while the transition to LUMO+1 is in y-axis direction. The presence of tert-butyl substituents does not affect the molecular orbitals shape, but affect their energies. Aggregation studies in dimethyl sulfoxide (DMSO):water solutions showed that naphthalocyanines studied have more aggregation tendency than the phthalocyanines. DFT studies indicated that stacked-dimers are preferred to rotated-stacked conformation due the interaction between ZnII and nitrogen atom from different monomers.

Synthesis and characterization of zinc naphthalocyanine derivative with potential application in photodynamic therapy

We report the synthesis and characterization of phthalocyanine–naphthalocyanine hybrids and the impact of the extended π-conjugation on the macrocycles aggregation, singlet oxygen production, fluorescence lifetime and quantum yields in solution. We observed that the addition of naphthalol units in the structure causes a bathochromic shift in UV-vis, emission and excitation bands and decreases the quantum yield of singlet oxygen in solution.

Enhancement of photodynamic therapy effects with mitochondrial reactive oxygen species

Enhancement of photodynamic therapy effects with mitochondrial reactive oxygen species

Synthesis and characterization of novel symmetrical and asymmetrical carboxyphthalocyanines with potential application in photodynamic therapy

Synthesis and characterization of novel symmetrical and asymmetrical carboxyphthalocyanines with potential application in photodynamic therapy

Some Phthalocyanine and Naphthalocyanine Derivatives as Corrosion Inhibitors for Aluminium in Acidic Medium: Experimental, Quantum Chemical Calculations, QSAR Studies and Synergistic Effect of Iodide Ions.

The effects of seven macrocyclic compounds comprising four phthalocyanines (Pcs) namely 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (Pc1), 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (Pc2), 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (Pc3) and 29H,31H-phthalocyanine (Pc4), and three naphthalocyanines namely 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (nPc1), 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (nPc2) and 2,3-naphthalocyanine (nP3) were investigated on the corrosion of aluminium (Al) in 1 M HCl using a gravimetric method, potentiodynamic polarization technique, quantum chemical calculations and quantitative structure activity relationship (QSAR). Synergistic effects of KI on the corrosion inhibition properties of the compounds were also investigated. All the studied compounds showed appreciable inhibition efficiencies, which decrease with increasing temperature from 30 °C to 70 °C. At each concentration of the inhibitor, addition of 0.1% KI increased the inhibition efficiency compared to the absence of KI indicating the occurrence of synergistic interactions between the studied molecules and I− ions. From the potentiodynamic polarization studies, the studied Pcs and nPcs are mixed type corrosion inhibitors both without and with addition of KI. The adsorption of the studied molecules on Al surface obeys the Langmuir adsorption isotherm, while the thermodynamic and kinetic parameters revealed that the adsorption of the studied compounds on Al surface is spontaneous and involves competitive physisorption and chemisorption mechanisms. The experimental results revealed the aggregated interactions between the inhibitor molecules and the results further indicated that the peripheral groups on the compounds affect these interactions. The calculated quantum chemical parameters and the QSAR results revealed the possibility of strong interactions between the studied inhibitors and metal surface. QSAR analysis on the quantum chemical parameters obtained with B3LYP/6-31G (d,p) method show that a combination of two quantum chemical parameters to form a composite index provides the best correlation with the experimental data.

Potentiometric multi-walled carbon nanotube Zn-sensor based on a naphthalocyanine neutral carrier: experimental and theoretical studies

Naphthalocyanine derivative is incorporated in carbon paste electrode and examined as a neutral carrier for zinc selective electrode.

Near-IR dye sensitization of polymer blend solar cells

We have fabricated ternary blend solar cells based on poly(3-hexylthiophene) (P3HT) as a donor material, poly{[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} (N2200) as an acceptor material, and a silicon naphthalocyanine derivative (SiNc) as a near-IR sensitizer. In order to discuss how molecular structures impact the dye sensitization in P3HT/N2200 solar cells, we studied two SiNc molecules with different axial groups: SiNc10 with decyldimethylsilyl oxide and SiNc6 with trihexylsilyl oxide. As a result, P3HT/N2200/SiNc10 ternary solar cells exhibited a power conversion efficiency of 1.4%, which is improved by 73% compared to P3HT/N2200 binary solar cells and also by 17% compared to P3HT/N2200/SiNc6 ternary solar cells. We discuss the origin of the improvement in the device performance in terms of dye location in ternary blend films.

Comparison of Two New Substituted Iron Phthalocyanines as Electrocatalysts for the Oxygen Reduction and Hydrazine Oxidation Reaction

In this work, two newly synthesized iron phthalocyanines (FePc's), with de-activating substitutents, iron(II) 2,9,16,23-tetra-tert-butyl-phthalocyanine (FePc(tBu)4), and its' naphthalocyanine derivative, iron(II) 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (FeNpPc(tBu)4), were evaluated as both oxygen (O2) reduction, and hydrazine (N2H4) oxidation electrocatalysts in acidic as well as basic media, respectively. Their UV-Vis spectra were compared, followed by surface wave cyclic voltammograms in a N2 purged acidic electrolyte. Their activities were compared to those of the unsubstituted or baseline FePc using rotating disk electrode (RDE), rotating ring disk electrode (RRDE) and cyclic voltammetry (CV) techniques. The resulting Tafel and Koutecky-Levich analyses confirmed the predicted activities towards both reactions to be FePc > FePc(tBu)4 > FeNpPc(tBu)4. However, a change in the FeNpPc(tBu)4 O2 reduction reaction (ORR) mechanism, as well as its' low activity towards N2H4 oxidation was also observed, demonstrating unexpected electronic and steric effects.

Third-order optical nonlinearities of naphthalocyanine derivatives measured by resonant femtosecond degenerate four-wave mixing technique

The third-order optical nonlinearities of several naphthalocyanine derivatives were measured under resonant conditions by the femtosecond degenerate four-wave mixing (DFWM) technique. Temporal profiles of the DFWM signal were measured with a time resolution of 0.3 ps, and were found to consist of at least two components, the coherent instantaneous nonlinear response and the slow response with a decay time constant longer than several hundred picoseconds. The latter can be attributed to the long-lived excited state and molecular rotational relaxation. The electronic molecular hyperpolarizability, γ e, was evaluated to be in the range (2.1–7.5) × 10 −29 esu for these macrocycles, two orders of magnitude greater than the nonresonant values.

Third-Order Optical Nonlinearities of Naphthalocyanine-Derivative-Doped Polymer Films Measured by Resonant Femtosecond Degenerate Four-Wave Mixing

Third-order optical nonlinearities of several polymer films doped with naphthalocyanine derivatives have been measured under resonant conditions by femtosecond degenerate four-wave mixing (DFWM). The metal substitution and the peripheral groups influence both the magnitude and the response of the third-order optical nonlinearities. Temporal profiles of the DFWM signal were measured with a time resolution of 0.3 ps and were found to consist of at least two components, the coherent instantaneous nonlinear response and the slow response. The latter for the films decayed much faster than that for the solutions due to effects of aggregation or intermolecular interactions. The electronic component of the effective third-order nonlinear optical suscepitibilities, χe(3), of the polymer films was evaluated and a film of poly(methyl methacrylate) doped with 20 wt% octabutoxy-substituted zinc 2,3-naphthalocyanine showed the largest χe(3) value of 8.9×10-9 esu. The results were compared with those in the literature.

Organic Thin Film Solar Cell

The present invention aims to provide an organic thin-film solar cell that has a high photoelectric conversion efficiency and excellent durability. The present invention is an organic thin-film solar cell including a photoelectric conversion layer, wherein the photoelectric conversion layer includes a portion containing a sulfide of a Group 15 element in the periodic table and an organic semiconductor portion contacting with each other, and the organic semiconductor portion comprises an organic semiconductor, the organic semiconductor comprising a polythiophene derivative, a phthalocyanine derivative, a naphthalocyanine derivative, or a benzoporphyrin derivative.

Preparation, characterization and gas sensitivity of copper naphthalocyanine derivatives LB films

Octaethyoxyl-2,3-naphthalocyanine and octabutoxy-2,3-naphthalocyanine copper (II) Langmuir monolayers were obtained at air–water interface. The aggregate forms of CuNc(OC 4H 9) 8 in chloroform solution at different aging times were studied. The CuNc(OC 2H 5) 8 and CuNc(OC 4H 9) 8 molecules were successfully transferred onto the solid substrate as Y-type mode by LB technique. The structure of LB films was characterized by IR and electronic spectra. The results show that the CuNc(OC 2H 5) 8 and the CuNc(OC 4H 9) 8 molecules were mainly arranged as J-aggregate in the film. The gas sensitivity of the films to alcohols with different chain lengths was measured at room temperature. The octaethyoxyl-2,3-naphthalocyanine LB films exhibit good sensitivity and good selectivity to propyl alcohol (10–30 ppm). This indicates that CuNc(OC 2H 5) 8 can be exploited as ambient alcohol sensor.

Third-order nonlinear optical properties of porphyrazine, phthalocyanine and naphthalocyanine germanium derivatives: Demonstrating the effect of π-conjugation length on third-order optical nonlinearity of two-dimensional molecules

Optical and third-order nonlinear optical properties of germanium porphyrazine, phthalocyanine and naphthalocyanine derivatives have been measured in order to evaluate the effect of extended π-electron conjugation on third-order optical nonlinearity. Third-order nonlinear optical susceptibilities χ (3) of thin films of trans-dihydroxy-1,6,11,16-tetra-( tert.butyl)porphyrazine germanium [ t-Bu 4PazGe(OH) 2], trans-dihydroxy-tetra-( tert.butyl)phthalocyaninato germanium [( t-Bu 4PcGe(OH) 2] and naphthalocyanine germanium (GeNc) derivative measured by the third-harmonic generation technique are reported. A χ (3)(−3 ω; ω, ω, ω) value as high as 1.3×10 −11 esu at 1.65 μm was observed for [ t-Bu 4PazGe(OH) 2] thin films from a dominant three-photon resonance. A χ (3)(−3 ω; ω, ω, ω) value of 2.5×10 −11 esu and a χ (3)/ α value of 1.65×10 −15 esu cm as figure of merit was observed for [ t-Bu 4PcGe(OH) 2] thin films at 1.8 μm. The χ (3) values of germanium porphyrazine derivative have been compared with those of structurally related germanium phthalocyanine and naphthalocyanine analogues to evaluate the effect of extended π-conjugation introduced through benzo substitution. A progressive red-shift in optical absorption peaks in the Q-band region and an increase in the third-order nonlinear optical susceptibility was noticed with sequential increase of benzo substitution from the porphyrazine to naphthalocyanine ring. The effect of benzo substitution as well as axial substitution on optical and third-order nonlinear optical properties has been discussed. Attempts have also been made to establish a correlation between third-order optical nonlinearity and photoconductivity of metallophthalocyanines in view of the present results.

Large Third-order Optical Non-linearities of Spin-cast Thin Films of Novel Metallo-naphthalocyanines

Third-order non-linear optical susceptibilities of silicon, germanium, tin, aluminum, manganese and vanadium naphthalocyanine derivatives measured by third-harmonic generation technique from 1.05 μm to 2.1 μm are reported. Our results show the dependence of χ(3)(–3ω;ω,ω,ω) values on the variation of the central metal atom associated to different metal-ligand charge-transfer interactions. Silicon naphthalocyanines ( SiNc ) showed the χ(3)(–3ω;ω,ω,ω) values on the order of 10−10 esu at 1.5 μm, this does not appear to be due to a three-photon resonance, instead the increase in χ(3) could be the two-photon resonance lying just above the one-photon state. Degenerate four-wave mixing measurements on thin films of a SiNc derivative yielded the χ(3)(–3ω;ω,ω,ω) value as high as 5.0 × 10−7 esu at 800 nm, enhanced by one-photon resonance near the Q-band peak region. The figure of merit χ(3)/α at 800 nm is quite large corresponding to 4.2 × 10−12 esu cm. Effect of the metal atoms and plausible resonance contribution accounting for large third-order optical non-linearity of naphthalocyanines are discussed.

Macrocyclic functional dyes: Applications to optical disk media, photochemical hole burning and non-linear optics

Abstract

Effect of Delivery System on the Pharmacokinetics and Tissue Distribution of bis(Di‐lsobutyl Octadecylsiloxy)Silicon 2,3‐Naphthalocyanine (isoBOSINC), a Photosensitizer for Tumor Therapy

Bis(di-isobutyl octadecylsiloxy)silicon 2,3-naphthalocyanine (isoBOSINC) is a representative of a group of naphthalocyanine derivatives with spectral and photophysical properties that make them attractive candidates for photodynamic therapy (PDT). Tissue distributions were studied in tumor-bearing rats as a function of delivery system and time following administration. The tumor model was an N-(4-[5-nitro-2-furyl]-2-thiazolyl) formamide (FANFT)-induced urothelial cell carcinoma transplanted into one hind leg of male Fischer 344 rats; isoBOSINC was delivered to the rats by intravenous injection of 0.50 mg/kg of body weight as a suspension either in 10% Tween 80 in saline (Tween) or 10% (Cremophor EL + propylene glycol) in saline (Cremophor). The isoBOSINC was isolated from several tissues and organs, as well as tumors and peritumoral muscles and skin. Quantitation was by a high-performance liquid chromatographic technique with detection that utilizes the native fluorescence of the naphthalocyanine derivative. Independent of the delivery system, the dye was retained in tumors at higher concentrations than in normal tissues, except for spleen and liver. The isoBOSINC retention in tumors was high and was vehicle dependent. For Tween, the maximal ratio of dye in tumor versus peritumoral muscle occurred 12 h after injection; for Cremophor, the maximal ratio occurred later, 336 h postinjection. When the drug was delivered in Tween, isoBOSINC in serum showed two compartment kinetics: half-lives of about 2 and 11 h were found for the distribution and the elimination phases, respectively. When Cremophor was the vehicle, the elimination half-life was about 20 h, and one compartment kinetics was observed. The latter findings may explain the generally higher levels of the dye attained by the tissues at later times with Cremophor as the vehicle. An interesting exception was that after 7 and 14 days postinjection in Tween, the levels of dye found in testes were six- to seven-fold higher than those found after Cremophor delivery. Levels of dye were very low or not detectable in the brain. Optimal parameters for PDT of tumors with this novel photosensitizer are clearly time- and vehicle-dependent, and future PDT studies will need to incorporate these modulators.