Highly Efficient Synthesis of Chloro‐ and Phenoxy‐Substituted Subphthalocyanines

Claessens, Christian G.; González‐Rodríguez, David; Rey, B. del; Torres, Tomás; Mark, Gertraud; Schuchmann, Heinz‐Peter; Sonntag, Clemens von; MacDonald, J. Gavin; Nohr, Ronald S.

doi:10.1002/ejoc.200300169

Cited by 145 publications

(188 citation statements)

References 14 publications

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“…Monoiodo-SubPcs 4 a-d (Scheme 1) were likewise obtained by statistical condensation of the two corresponding phthalonitrile derivatives in the presence of boron trichloride in p-xylene at reflux. [17] Most compounds and isomers could be isolated from the resulting reaction mixture by column chromatography on silica gel with appropriate eluents. [18] Unlike Pcs, SubPcs yield quite informative NMR spectra, which helped in the identification of the desired isomers.…”

Section: Introductionmentioning

confidence: 99%

Tuning Photoinduced Energy‐ and Electron‐Transfer Events in Subphthalocyanine–Phthalocyanine Dyads

González‐Rodríguez

Claessens

Torres

et al. 2005

Chemistry A European J

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112

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A series of subphthalocyanine-phthalocyanine dyads has been prepared by means of palladium-catalyzed cross-coupling reactions between a monoalkynylphthalocyanine and different monoiodosubphthalocyanines. Electronic coupling between the two photoactive units is ensured by a rigid and pi-conjugated alkynyl spacer. In addition, the electronic characteristics of the subphthalocyanine moiety were modulated by the introduction of different peripheral substituents. Cyclic and Osteryoung square-wave voltammetry experiments revealed that the reduction potential of this subunit can be decreased by about 400 mV on going from thioether or no substituents to nitro groups. As a consequence, the energy level of the charge-transfer state could be fine-tuned so as to gain control over the fate of the photoexcitation energy in each subunit. The diverse steady-state and time-resolved photophysical techniques employed demonstrated that, when the charge-transfer state lies high in energy, a quantitative singlet-singlet energy-transfer mechanism from the excited subphthalocyanine to the phthalocyanine takes place. On the contrary, stabilization of the radical pair by lowering the redox gap between electron donor and acceptor results in a highly efficient photoinduced electron-transfer process, even in solvents of low polarity such as toluene (Phi(ET) approximately 0.9). These features, together with the extraordinary absorptive cross section that these molecular ensembles display across the whole UV/Vis spectrum, make them model candidates for application in situations where broadband light sources are needed.

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Section: Introductionmentioning

confidence: 99%

Tuning Photoinduced Energy‐ and Electron‐Transfer Events in Subphthalocyanine–Phthalocyanine Dyads

González‐Rodríguez

Claessens

Torres

et al. 2005

Chemistry A European J

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112

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“…[ 17 ] Treatment of 4,5-dichlorophthalonitrile in p -xylene at 140 ° C in the presence of BCl 3 produced Cl 6 -SubPc in 56% yield after column chromatography. Similarly, F 6 -SubPc and F 3 -SubPc were prepared from 4,5-difl uorophthalonitrile and 4-fl uoro-phthalonitrile respectively.…”

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confidence: 99%

“…Similarly, F 6 -SubPc and F 3 -SubPc were prepared from 4,5-difl uorophthalonitrile and 4-fl uoro-phthalonitrile respectively. F 3 -SubPc was produced as a 3:1 mixture of C 1 and C 3 -isomers, [ 17 ] and used as such in subsequent studies. Full details are provided in the Supporting Information.…”

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confidence: 99%

Halogenated Boron Subphthalocyanines as Light Harvesting Electron Acceptors in Organic Photovoltaics

Sullivan

Duraud

Hancox

et al. 2011

Advanced Energy Materials

152

165

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The fi eld of organic photovoltaics (OPVs) is attracting enormous interest due to its promise of providing a low-cost, easily processable technology for energy generation. Whilst the shortcircuit current density ( J SC ) of OPV devices can be optimized through morphology control, [ 1 ] intermixing, [ 2 , 3 ] nanostructuring [ 4 ] or templating [ 5 ] amongst other techniques, the opencircuit voltage ( V OC ) is critically dependent on the choice of photoactive materials. The relative abundance of suitable commercially available materials has led to a wealth of reports on optimization of the donor layer; [ 6 , 7 ] however the same is not true for the acceptor layer, with most work focusing on the ubiquitous fullerenes. Whilst fullerenes are undoubtedly effi cient electron transport materials, this class of acceptor material has inherent issues with long-term stability [ 8 , 9 ] and relatively low bandgaps which limit the maximum obtainable V OC in single heterojunction systems. [ 10 ] Overcoming these issues by use of alternative acceptor materials, whilst maintaining or improving overall effi ciencies, is an important challenge in the OPV fi eld.Initially, the V OC in OPVs was believed to be primarily limited by the work function difference between the two electrodes, however, it has since become clear that the difference in energy between the highest occupied molecular orbital (HOMO) of the donor (D) and the lowest unoccupied molecular orbital (LUMO) of the acceptor (A), i.e. the interface gap ( I G ), is the primary determinant of the maximum V OC obtained. [ 6 , 11 ] Importantly, the frontier orbital energies of organic materials can be readily tuned through introduction of electron-donating or electron-withdrawing substituents. For example, halogenation of conjugated molecules has been shown to lower the HOMO and LUMO levels with respect to the vacuum level whilst having only a small effect on other electronic properties such as the bandgap, or the position of the Fermi level within the bandgap. [ 12 , 13 ] As an example of the extent of modifi cation possible by this method, complete fl uorination of copper phthalocyanine (CuPc) to its hexadecafl uoro derivative (F 16 CuPc) results in a shift of the HOMO level by over 1 eV. [ 14 ] The D/A heterojunction system of boron subphthalocyanine chloride (SubPc)/fullerene (C 60 ) is amongst the current fi eld-leaders for single small molecule heterojunction devices both in terms of V OC ( ∼ 1.1 V) and overall power conversion effi ciency ( PCE ∼ 3%). [ 15 , 16 ] However, consideration of the interfacial energetics of this system reveals that C 60 is far from optimal as the acceptor (vide infra). In this communication, we report the synthesis of several new selectively chlorinated and fl uorinated SubPcs, and demonstrate that effi cient OPV devices can be constructed using these materials as electron acceptors. Moreover, it is shown that peripheral halogenation can be used to maximize the interface gap, and hence the V OC obtained. As well as a remarkably high V ...

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“…[15] 4-(4-Biphenylphenoxy)phthalonitrile 3 was obtained in 40% yield by Suzuki cross-coupling reaction between 4-(4-bromophenylphenoxy)phthalonitrile 4 and phenylboronic acid in the presence of tetrakis(triphenylphosphine) palladium as catalyst in DME. [16] SubPc 1 was purified by silica gel column chromatography and characterized by 1 H NMR spectroscopy, UV-Vis spectrophotometry, MALDI-TOF mass spectrometry, and FTIR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Subphthalocyanine-Based Stopcock for Zeolite L

Ince¹,

Claessens²,

Brühwiler³

et al. 2011

MHC

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Highly Efficient Synthesis of Chloro‐ and Phenoxy‐Substituted Subphthalocyanines

Cited by 145 publications

References 14 publications

Tuning Photoinduced Energy‐ and Electron‐Transfer Events in Subphthalocyanine–Phthalocyanine Dyads

Tuning Photoinduced Energy‐ and Electron‐Transfer Events in Subphthalocyanine–Phthalocyanine Dyads

Halogenated Boron Subphthalocyanines as Light Harvesting Electron Acceptors in Organic Photovoltaics

Synthesis of Subphthalocyanine-Based Stopcock for Zeolite L

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