Self-Assembled Monolayers of Subphthalocyanines on Gold Substrates

González‐Rodríguez, David; Martínez‐Díaz, M. Victoria; Abel, Julia; Perl, András; Huskens, Jurriaan; Echegoyen, Luís; Torres, Tomás

doi:10.1021/ol100984d

Cited by 21 publications

(14 citation statements)

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“…5 However, BsubPc is highly substitutable, both at the axial position and around the periphery. 6 More recently, a number of substituted BsubPcs have been reported and characterized, including halides, 6 pseudohalides, 7 phenols, [8][9][10][11][12] bisphenols, 13 alcohols 14,15 and phthalimides. 16 Although frequently observed as a byproduct of BsubPc reactions [16][17][18][19] and known to have unique spectroscopic properties amongst the BsubPcs, 20 there are very few reports concerning the synthesis or study of the oxygen bridged dimer, μ-oxo-(BsubPc) 2 (Fig.…”

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Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)₂s)

et al. 2015

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A process for the gram scale synthesis of the oxygen bridged dimer of boron subphthalocyanine, μ-oxo-(BsubPc)2, has been developed. During the development it was found that a wide range of reaction pathways under diverse conditions lead to μ-oxo-(BsubPc)2 formation. However, obtaining μ-oxo-(BsubPc)2 as the main reaction product in appreciable yields and its subsequent isolation were extremely challenging. The best balance of purity, yield and conversion was achieved with a time controlled reaction of an equimolar reaction of HO-BsubPc with Br-BsubPc in the presence of K3PO4. The purification involved sequentially Soxhlet extraction, Kauffman column chromatography and train sublimation. We have repeated the process and yields ranged from 27 to 30% of pure, doubly-sublimed μ-oxo-(BsubPc)2. This process also enabled the synthesis of unsymmetric μ-oxo-(BsubPc)2s by reaction of HO-BsubPc with Br-F12BsubPc, Cl-Cl6BsubPc and Cl-Cl12BsubPc. After synthesis the solution-state properties of the unsymmetric μ-oxo-(BsubPc)2s were investigated, and compared to the symmetric μ-oxo-(BsubPc)2 and more broadly to other BsubPcs. The electronic properties of μ-oxo-(BsubPc)2 were found to differ from its unsymmetric counterparts, but were found to be similar to halo-BsubPcs. Furthermore, the photophysical properties of μ-oxo-(BsubPc)2, both symmetric and unsymmetric, differed greatly from all other known BsubPcs.

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confidence: 99%

Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)₂s)

et al. 2015

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“…A loss of the axial Cl ligand upon adsorption on gold is highly unlikely, since such a process has never been observed for Cl [8a,8b,8d,11] or other, more extended ligands. [4,9,12] Thirdly, the SAM contains small amounts of oxygen. Oxygen contaminations are commonly observed in oligodentate thioether-based SAMs.…”

Section: Resultsmentioning

confidence: 99%

“…[4,8b,9] However, the molecular mechanisms by which these binding units interact with gold surfaces and assemble into closed monolayer films when undisturbed by elaborate axial ligands are still unknown. Here we describe the adsorption of two subphthalocyaninatoboron derivatives [BCl{Subpc’(SR) 6 }] (Fig.…”

Section: Introductionmentioning

confidence: 99%

Molecular Suction Pads: Self‐Assembled Monolayers of Subphthalocyaninatoboron Complexes on Gold

et al. 2013

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Subphthalocyaninatoboron complexes with six long-chain alkylthio substituents in their periphery are applicable for the formation of self-assembled monolayers (SAMs) on gold. Such films were prepared from solution with the axially chlorido substituted derivatives and characterised by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results are in accord with the formation of SAMs assembled by the chemisorption of both covalently bound thiolate-type as well as coordinatively bound thioether units. The adsorbate molecules adopt an essentially ‘flat’ adsorption geometry on the substrate, resembling a suction pad on a surface.

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“…Therefore the triscyclopropanation reactions leading to C 60 -S-C/C 60 -S-Fc-C and to C 60 -S-O/C 60 -S-Fc-O were found to proceed with the same regio-and diastereoselectivity for each tether. In order to ascertain the binding patterns to the fullerene in the trisadducts, we studied the products by NMR spectroscopy ( 1 H, 13 C, HMQC and NOESY NMR) and performed molecular modeling studies using a combination of semiempirical (PM3) and density functional theory (DFT; B3LYP/3-21G) methods. 15 When the linker is connected to the SubPc macrocycle via a C-C bond (-C series), the trisaddition reaction between S-Fc-C or S-C and C 60 at 20°C yields a 5:95 mixture of two regioisomers (r and , respectively; Figures 1, and Figures S1-S4, Supporting Information) that could be separated by successive flash column chromatographies.…”

Section: Resultsmentioning

confidence: 99%

Activating Multistep Charge-Transfer Processes in Fullerene−Subphthalocyanine−Ferrocene Molecular Hybrids as a Function of π−π Orbital Overlap

et al. 2010

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We have synthesized two different fullerene-subphthalocyanine-ferrocene conjugates. The molecules were designed so that the ferrocene unit is linked at the subphthalocyanine axial position through a phenoxy spacer while the C(60) is rigidly held close to the concave face of the macrocycle via a 3-fold C(3)-symmetrical anchoring. The Bingel trisaddition reaction leading to the final products proceeded with very high regioselectivities and full diastereoselectivity. The only difference between both systems is the length of the triple tether employed, which finely regulates the regioselectivity of the trisaddition reaction and the distance between the subphthalocyanine and the C(60) complementary π-π surfaces. Thus, when the tether is connected to the subphthalocyanine through a direct C-C bond, a short π-π distance of 3.25-3.30 Å was calculated. In contrast, when it is connected through a slightly longer C-O-C bond, the distance increases to 3.5-3.6 Å. This π-π distance has a strong influence on the ground-state electronic interactions between the subphthalocyanine and the C(60), as determined from electronic absorption and cyclic voltammetry measurements. In addition, fluorescence and time-resolved transient absorption experiments demonstrated that different mechanisms operate in the two systems after photoexcitation. Despite the similar HOMO-LUMO gaps, only when the two complementary π-π surfaces of the subphthalocyanine and the C(60) are held at a close distance, therefore showing a high degree of orbital overlap, is a multistep electron transfer process triggered, ultimately leading to the long-lived, spatially separated C(60) radical anion and ferrocenium radical cation pair. A full account of the synthesis, characterization, and studies of the ground- and excited-state electronic interactions occurring in these conjugates, as well as in their reference C(60)-subphthalocyanine and subphthalocyanine-ferrocene dyads, is presented in this article.

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Self-Assembled Monolayers of Subphthalocyanines on Gold Substrates

Abstract: A series of dithiolane-substituted subphthalocyanines have been synthesized that can form self-assembled monolayers on gold surfaces, as confirmed by diverse characterization techniques.

Cited by 21 publications

References 30 publications

Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)₂s)

Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)₂s)

Molecular Suction Pads: Self‐Assembled Monolayers of Subphthalocyaninatoboron Complexes on Gold

Activating Multistep Charge-Transfer Processes in Fullerene−Subphthalocyanine−Ferrocene Molecular Hybrids as a Function of π−π Orbital Overlap

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Self-Assembled Monolayers of Subphthalocyanines on Gold Substrates

Abstract: A series of dithiolane-substituted subphthalocyanines have been synthesized that can form self-assembled monolayers on gold surfaces, as confirmed by diverse characterization techniques.

Cited by 21 publications

References 30 publications

Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)2s)

Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)2s)

Molecular Suction Pads: Self‐Assembled Monolayers of Subphthalocyaninatoboron Complexes on Gold

Activating Multistep Charge-Transfer Processes in Fullerene−Subphthalocyanine−Ferrocene Molecular Hybrids as a Function of π−π Orbital Overlap

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Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)₂s)

Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo-(BsubPc)₂s)