36530-06-0Relevant articles and documents
Ultrafast Excimer Formation and Solvent Controlled Symmetry Breaking Charge Separation in the Excitonically Coupled Subphthalocyanine Dimer
Roy, Palas,Bressan, Giovanni,Gretton, Jacob,Cammidge, Andrew N.,Meech, Stephen R.
, p. 10568 - 10572 (2021)
Knowledge of the factors controlling excited state dynamics in excitonically coupled dimers and higher aggregates is critical for understanding natural and artificial solar energy conversion. In this work, we report ultrafast solvent polarity dependent excited state dynamics of the structurally well-defined subphthalocyanine dimer, μ-OSubPc2. Stationary electronic spectra demonstrate strong exciton coupling in μ-OSubPc2. Femtosecond transient absorption measurements reveal ultrafast excimer formation from the initially excited exciton, mediated by intramolecular structural evolution. In polar solvents the excimer state decays directly through symmetry breaking charge transfer to form a charge separated state. Charge separation occurs under control of solvent orientational relaxation.
Dual Role of Subphthalocyanine Dyes for Optical Imaging and Therapy of Cancer
van de Winckel, Eveline,Mascaraque, Marta,Zamarrón, Alicia,Juarranz de la Fuente, ángeles,Torres, Tomás,de la Escosura, Andrés
, (2018)
The family of subphthalocyanine (SubPc) macrocycles represents an interesting class of nonplanar aromatic dyes with promising features for energy conversion and optoelectronics. The use of SubPcs in biomedical research is, on the contrary, clearly underexplored, despite their documented high fluorescence and singlet oxygen quantum yields. Herein, for the first time it is shown that the interaction of these chromophores with light can also be useful for theranostic applications, which in the case of SubPcs comprise optical imaging and photodynamic therapy (PDT). In particular, the article evaluates, through a complete in vitro study, the dual-role capacity of a novel series of SubPcs as fluorescent probes and PDT agents, where the macrocycle axial substitution determines their biological activity. The 2D and 3D imaging of various cancer cell lines (i.e., HeLa, SCC-13, and A431) has revealed, for example, different subcellular localization of the studied photosensitizers (PS), depending on the axial substituent they bear. These results also show excellent photocytotoxicities, which are affected by the PS localization. With the best dual-role PS, preliminary in vivo studies have demonstrated their therapeutic potential. Overall, the present paper sets the bases for an unprecedented biomedical use of these well-known optoelectronic materials.
Synthesis of phthalonitrile derivatives by photoinduced reactions. New unsymmetrical substituted zinc phthalocyanines
Tempesti, Tomas C.,Baumgartner, María T.
, p. 1088 - 1094 (2015)
The synthesis of new phthalonitrile derivatives by photoinduced reaction is described. Novel unsymmetrically substituted Zn(II) phthalocyanine bearing an aryl alcohol group (ArZnPc) was synthesized by the ring expansion reaction of boron(III) subphthalocyanine chloride with an appropriated phthalonitrile. The spectroscopic and photodynamic properties of these ArZnPc were studied.
Third Harmonic Generation Spectroscopy of Boron Subphthalocyanine
Diaz-Garcia, Maria A.,Agullo-Lopez, Fernando,Sastre, Angela,Torres, Tomas,Torruellas, William E.,Stegeman, George I.
, p. 14988 - 14991 (1995)
The dispersive behavior of the magnitude and phase of χ3(-3ω: ω,ω,ω) of sublimated boron subphthalocyanine (SubPc) thin films has been investigated via third harmonic generation (THG) spectroscopy in the range 950-2000 nm. χ3 values, three times bigger than those obtained for phthalocyanines in the same frequency range, have been measured.A four-level model, including the ground state and three excited states associated to bands observed in the linear absorption spectrum, has been succesfully used to explain the nonlinear behavior of these compounds.
Synthesis of unsymmetrical benzoporphyrazines in functional ionic liquids and formation of self-aggregates of zinc(II) pyridino[3,4]tribenzoporphyrazines in solutions
Chauhan,Kumari, Pratibha
, p. 2518 - 2524 (2009)
Unsymmetrically substituted metal-free and metallated benzoporphyrazines including pyridino[3,4]tribenzoporphyrazinic macrocycles have been synthesized in good yields by ring expansion reactions of boron(III) subphthalocyanines with phthalonitriles in functional ammonium ionic liquids in the presence of 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) under different reaction conditions. The concentration dependent UV/vis, fluorescence, NMR and ESI-MS spectroscopic data indicate that zinc(II) pyridino[3,4]tribenzoporphyrazines exist as head-to-tail self-aggregates in the solution phase.
Synthesis and STM imaging of symmetric and dissymmetric ethynyl-bridged dimers of boron-subphthalocyanine bowl-shaped nanowheels
Jacquot De Rouville, Henri-Pierre,Garbage, Romain,Ample, Francisco,Nickel, Anja,Meyer, Joerg,Moresco, Francesca,Joachim, Christian,Rapenne, Gwéna?l
, p. 8925 - 8928 (2012)
The future's wheel: A new class of wheels, based on subphthalocyanine fragments, for future incorporation in functional nanovehicles is reported (see figure). The syntheses of a symmetric wheel, a nitrogen-tagged wheel, and their ethynyl-bridged homodimers are presented. Theoretical calculations and STM imaging demonstrate the advantage of a bowl-shaped structure and the efficiency of the tag for STM imaging.
Synthesis, spectroscopy, electrochemistry and DFT of electron-rich ferrocenylsubphthalocyanines
Conradie, Jeanet,Swarts, Pieter J.
supporting information, (2020/07/02)
A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H)12 with ferrocenylcarboxylic acids Y-H = (FcCH2CO2-H), (Fc(CH2)3CO2-H) or (FcCO(CH2)2CO2-H) in the axial position were synthesized from the parent Cl-BSubPc(H)12 via an activated triflate-SubPc intermediate. UV/Vis data revealed that the axial ferrocenyl-containing ligand did not influence the Q-band maxima compared to Cl-BSubPc(H)12. A combined electrochemical and density functional theory (DFT) study showed that Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the macrocycle of the subphthalocyanine. Both observed reductions were ring-based. It was found that the novel Fc(CH2)3CO2BSubPc(H)12 exhibited the lowest first macrocycle-based reduction potential (-1.871Vvs. Fc/Fc+) reported for SubPcs till date. The oxidation and reduction values of Fc(CH2)nCO2BSubPc(H)12 (n = 0-3), FcCO(CH2)2CO2BSubPc(H)12, and Cl-BSubPc(H)12 illustrated the electronic influence of the carboxyl group, the different alkyl chains and the ferrocenyl group in the axial ligand on the ring-based oxidation and reduction values of the SubPcs.
Pyrene/coumarine-subphthalocyanine conjugates as light harvesting systems with intramolecular energy transfer
Decréau, Richard A.,Lioret, Vivian,Rousselin, Yoann
, (2020/08/06)
A series of subphthalocyanine-antenna dyads have been successfully designed, synthetized and characterized by 1H NMR, 13C NMR, high-resolution mass spectroscopy and X-ray diffraction for some of them. Pyrene and coumarine have been appended at the axial position of the subphthalocyanine scaffold using different types of linkers. Photophysical properties of the new compounds have been measured in toluene, tetrahydrofuran, chloroform, dimethyl sulfoxide and methanol. Energy transfer efficiencies between antenna and the subphthalocyanine platform have been investigated and almost quantitative energy transfer occurs in the antenna-platform 5.
Addressing subphthalocyanines and subnaphthalocyanines features relevant to fluorescence imaging
Bernhard, Yann,Richard, Philippe,Decréau, Richard A.
, p. 1047 - 1052 (2018/02/06)
A series of new synthetic subphthalocyanines bear structural features aimed at allowing either fluorescence activation or a bathochromic shift of the absorption band towards the near-infrared window, relevant to optical imaging. X-ray diffraction studies of four subphthalocyanines are reported. Spectrofluorimetric studies on subnaphthalocyanines and activatable subphthalocyanine pro-fluorophores are reported.
Acetylenic Scaffolding with Subphthalocyanines
Gotfredsen, Henrik,Jevric, Martyn,Kadziola, Anders,Nielsen, Mogens Brondsted
, p. 17 - 21 (2016/01/20)
A new boron subphthalocyanine (SubPc) derivative with a terminal alkyne substituent on the central boron atom was prepared by substitution of a triflate at the boron atom with but-3-yn-1-ol. This compound was shown to be a versatile building block for metal-catalyzed coupling reactions, such as modified Glaser-Hay, Cadiot-Chodkiewicz, and Sonogashira reactions as well as the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). For example, metal-catalyzed reactions provided access to a SubPc dimer containing a butadiyne bridging unit, two different SubPc-fullerene dyads as well as two cross-conjugated SubPc-tetraethynylethene (TEE) scaffolds. These TEEs containing two silyl-protected alkyne units are potential building blocks for further acetylenic scaffolding. The work shows how the axial position is post-functionalized in steps not involving a substitution reaction at the central boron atom, which is otherwise often used as the terminal step in axial functionalization of SubPcs.
