- Ultrafast Excimer Formation and Solvent Controlled Symmetry Breaking Charge Separation in the Excitonically Coupled Subphthalocyanine Dimer
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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.
- Roy, Palas,Bressan, Giovanni,Gretton, Jacob,Cammidge, Andrew N.,Meech, Stephen R.
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- Dual Role of Subphthalocyanine Dyes for Optical Imaging and Therapy of Cancer
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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.
- van de Winckel, Eveline,Mascaraque, Marta,Zamarrón, Alicia,Juarranz de la Fuente, ángeles,Torres, Tomás,de la Escosura, Andrés
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- Synthesis of phthalonitrile derivatives by photoinduced reactions. New unsymmetrical substituted zinc phthalocyanines
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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.
- Tempesti, Tomas C.,Baumgartner, María T.
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- Third Harmonic Generation Spectroscopy of Boron Subphthalocyanine
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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.
- Diaz-Garcia, Maria A.,Agullo-Lopez, Fernando,Sastre, Angela,Torres, Tomas,Torruellas, William E.,Stegeman, George I.
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- Synthesis of unsymmetrical benzoporphyrazines in functional ionic liquids and formation of self-aggregates of zinc(II) pyridino[3,4]tribenzoporphyrazines in solutions
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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.
- Chauhan,Kumari, Pratibha
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- Synthesis and STM imaging of symmetric and dissymmetric ethynyl-bridged dimers of boron-subphthalocyanine bowl-shaped nanowheels
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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.
- Jacquot De Rouville, Henri-Pierre,Garbage, Romain,Ample, Francisco,Nickel, Anja,Meyer, Joerg,Moresco, Francesca,Joachim, Christian,Rapenne, Gwéna?l
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- Synthesis, spectroscopy, electrochemistry and DFT of electron-rich ferrocenylsubphthalocyanines
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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.
- Conradie, Jeanet,Swarts, Pieter J.
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supporting information
(2020/07/02)
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- Pyrene/coumarine-subphthalocyanine conjugates as light harvesting systems with intramolecular energy transfer
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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.
- Decréau, Richard A.,Lioret, Vivian,Rousselin, Yoann
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- Addressing subphthalocyanines and subnaphthalocyanines features relevant to fluorescence imaging
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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.
- Bernhard, Yann,Richard, Philippe,Decréau, Richard A.
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p. 1047 - 1052
(2018/02/06)
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- Acetylenic Scaffolding with Subphthalocyanines
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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.
- Gotfredsen, Henrik,Jevric, Martyn,Kadziola, Anders,Nielsen, Mogens Brondsted
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- Subphthalocyanine as hole transporting material for perovskite solar cells
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Non planar 14-π aromatic subphthalocyanine has been introduced for the first time as hole transporting material for organometal halide perovskite solar cells and achieved a power conversion efficiency of 6.6%. Cells stored in the dark under ambient conditions underwent an incubation period of nine days during which, we observed an increase in efficiency followed by slow progressive deterioration. However, Raman spectral analysis of pristine perovskite deposited on titania revealed a much faster degradation thus indicating that the subphthalocyanine layer provides a temporary protection to the underlying perovskite layer.
- Sfyri, Georgia,Kumar, Challuri Vijay,Sabapathi, Gokulnath,Giribabu, Lingamallu,Andrikopoulos, Konstantinos S.,Stathatos, Elias,Lianos, Panagiotis
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p. 69813 - 69818
(2015/09/01)
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- Harnessing medically relevant metals onto water-soluble subphthalocyanines: Towards bimodal imaging and theranostics
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Subphthalocyanine (SubPc), a putative fluorophore for optical imaging (OI), was conjugated to chelating ligands (DOTA, DTPA) affording water-soluble conjugates complexed with (non-radioactive) metals relevant to the following medical imaging techniques/therapies: MRI (Gd), PET (Cu, Ga), SPECT (In, Ga, Lu), RIT (Cu, Lu, Y), and NCT (Gd). Magneto-optical properties of ditopic gadolinium species (and optical properties of other metal containing species) were examined (brightness (ε × ΦF) and relaxivity R1) and fluorescence confocal/biphoton microscopy studies were conducted. This journal is
- Bernhard, Yann,Winckler, Pascale,Perrier-Cornet, Jean-Marie,Decrau, Richard A.
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p. 3200 - 3208
(2015/03/05)
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- Subphthalocyanines: Addressing water-solubility, nano-encapsulation and activation for optical imaging of B16 melanoma cells
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Water-soluble disulfonato-subphthalocyanines (SubPcs) or hydrophobic nano-encapsulated SubPcs are efficient probes for the fluorescence imaging of cells. 20 nm large liposomes (TEM and DLS) incorporated about 13% SubPc. Moreover, some of these fluorophores were found to be pH activatable.
- Bernhard, Yann,Winckler, Pascale,Chassagnon, Remi,Richard, Philippe,Gigot, lodie,Perrier-Cornet, Jean-Marie,Decrau, Richard A.
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supporting information
p. 13975 - 13978
(2015/02/19)
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- Trapping fullerenes with jellyfish-like subphthalocyanines
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Six electronically different concave-shaped subphthalocyanines (SubPcs) have been prepared for testing the structural factors governing fullerenes encapsulation. Thus, the supramolecular interaction of SubPcs with C 60 and C70 fuller
- Sanchez-Molina,Claessens,Grimm,Guldi,Torres
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p. 1338 - 1344
(2013/06/04)
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- Synthesis of symmetrical and unsymmetrical subphthalocyanine dimers containing a hydroquinone bridge
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Three novel hydroquinone-based symmetrically and unsymmetrically substituted subphthalocyanine (SubPc) dimers have been synthesized through the axial substitution of the macrocycle. The mono SubPc hydroquinone derivative (Hq-SubPc) first prepared acts as a nucleophile which replaces the chlorine atom of the second SubPc molecule to form the dimer. The dimers were obtained by reacting hydroquinone and the respective SubPcs in a 1:1 molar ratio in toluene at 180 °C in a pressure vessel. This new approach allowed stoichiometric quantities of reactants to be utilized. All dimers were characterized by 1H NMR, 13C NMR, UV-vis, fluorescence and mass spectral analysis.
- Viswanath, Lakshmi C. Kasi,Shirtcliff, Laura D.,Berlin, K. Darrell
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p. 1167 - 1172
(2014/01/17)
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- Subphthalocyanine derivatives having a phosphorus group as an axial substituent
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The synthesis and properties of novel subphthalocyanines having a phosphorus group as an axial substituent are reported. The excellent solubility of these materials may provide a good production method for optical films without impairing the excellent pro
- Yamasaki, Yasuhiro,Mori, Tomohiro
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supporting information; experimental part
p. 245 - 247
(2012/04/23)
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- Observations regarding the crystal structures of non-halogenated phenoxyboronsubphthalocyanines having para substituents on the phenoxy group
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We report the synthesis and systematic description of a series of five para-substituted phenoxy-BsubPcs including their characterization in the crystal state. The nature of the substituents on the phenoxy molecular fragment was chosen so as to vary both t
- Paton, Andrew S.,Morse, Graham E.,Lough, Alan J.,Bender, Timothy P.
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experimental part
p. 914 - 919
(2012/02/01)
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- μ-oxo-bridged subphthalocyanine dimers: Preparation and characterization by X-ray structure analysis
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In connection with our previous research on μ-oxo-bridged metal phthalocyanine dimers, we have synthesized μ-oxo-bridged subphthalocyanine dimers (μ-oxo subpc dimers) with various peripheral substituents and studied their properties. Compared to the corre
- Yamasaki, Yasuhiro,Mori, Tomohiro
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p. 1208 - 1214
(2012/01/31)
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- Chloro boron subphthalocyanine and its derivatives: Dyes, pigments or somewhere in between?
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Nine derivatives of chloro boron subphthalocyanine (Cl-BsubPc, 1) have been synthesized and characterized. Seven dimers of Cl-BsubPc have been synthesized by reaction with biphenol (2a), bisphenol A (2b), bisphenol F (2c), bisphenol O (2d), bisphenol P (2
- Morse, Graham E.,Paton, Andrew S.,Lough, Alan,Bender, Timothy P.
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experimental part
p. 3915 - 3922
(2010/07/04)
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- Self-assembled monolayers of subphthalocyanines on gold substrates
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A series of dithiolane-susbstituted subphthalocyanines have been synthesized that can form self-assembled monolayers on gold surfaces, as confirmed by diverse characterization techniques.
- Gonzalez-Rodriguez, David,Martinez-Diaz, M. Victoria,Abel, Julia,Perl, Andras,Huskens, Jurriaan,Echegoyen, Luis,Torres, Tomas
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supporting information; scheme or table
p. 2970 - 2973
(2010/09/07)
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- Ethynyl-boron subphthalocyanines displaying efficient cascade energy transfer and large stokes shifts
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A new class of luminescent dyes incorporates aromatic residues attached by an ethynyl link to the boron center of a subphthalocyanine (SubPc; see picture). Efficient energy transfer from energydonor subunits to the SubPc produces very large Stokes shifts,
- Camerel, Franck,Ulrich, Gilles,Retailleau, Pascal,Ziessel, Raymond
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supporting information; experimental part
p. 8876 - 8880
(2009/05/26)
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- Optical Layer including mu-oxo-bridged boron-subphthalocyanine dimer
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An optical layer comprises μ-oxo-bridged boron subphthalocyanine dimer. The μ-oxo-bridged boron subphthalocyanine dimer is represented by the following chemical formula (1). (In the chemical formula (1), Z1 to Z12 are the same or different to each other and selected from the groups consisting of a hydrogen atom, a hydroxyl group, a mercapto group, an alkyl group, an aralkyl group, an aryl group, an amino group, an alkoxyl group and a thioether group. Z1 to Z12 have one or more substitutional groups or have no substitutional group.)
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Page/Page column 7; 18
(2008/12/08)
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- Synthesis, electrochemical and photochemical properties of unsymmetrically substituted zinc phthalocyanine complexes
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The synthesis of symmetrically and unsymmetrically substituted zinc phthalocyanine (ZnPc) derivatives are reported. The ZnPc derivatives are synthesized by ring expansion of subphthalocyanine complexes. Ring substitution is effected with tert-butyl phenol
- Matlaba, Pulane,Nyokong, Tebello
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p. 2463 - 2472
(2008/10/08)
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- Synthesis and structural characterization of boron subphthalocyaninates
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Halosubphthalocyaninatoboron, [B(X)spc] (X = F, Cl, Br) is obtained by heating phthalonitrile with boron trihalide in quinoline (X = F) or the corresponding halobenzene, resp. [B(C6H5)spc] is prepared from phthalonitrile and tetraphenylborate or tetraphenyloboron oxide, resp. [B(OR)spc] (R = H, CH(CH3)2, C(CH3)3, C6H5) is synthesized by bromide substitution of [B(Br)spc] in pyridine/ HOR. Substitution of [B(Br)spc] in carboxylic acids yields [B(OOCR)spc] (R = H, CX3 (X = H, Cl, F), CH2X (X = Cl, C6H5), C6H5). All subphthalocyaninates are characterized electrochemically and by UV-VIS, IR/FIR, resonance Raman, and 1H/10B-NMR spectroscopy. Typical B-X stretching vibrations are at 622 (X = Br), 950 (Cl), 1063 (F), 1096 cm-1 (OH) as well as between 1119 and 1052 cm-1 (OR) resp. 985 and 1028cm-1 (OOCR). The difference v(C=O)-v(C-O) > 400 cm-1 confirms the unidentate coordination of the carboxylato ligands. According to the crystal structure analysis of [B(OH)s,pc], [B(OH)spc] · 2H2O, [B(C6H5)spc], [B(OC(CH3)3)spc], [B(OOCCH3)spc] · 0.5H2O · C2H5OH and [B(OOCCH3)spc] · 0.4H2O · 1.1 C5H5N the spc ligand is concavely distorted. This saucer shaped conformation is independent of the acido ligands and the presence of solvate. The outermost C atomes are vertically displaced in part by more than 2 A from the N, plane. The B atom is in a distorted tetrahedral coordination geometry. It is displaced by ca 0.64 A out of the NI plane towards the acido ligand. The average B-N distance is 1.500 A, and the B-O distances range from 1.418(5) to 1.473(2) A.
- Potz, Roland,Goeldner, Melanie,Hueckstaedt, Heiner,Cornelissen, Ursula,Tutass, Andreas,Homborg, Heiner
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p. 588 - 596
(2008/10/08)
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