Panchromatic light funneling through the synergy in hexabenzocoronene-(metallo)porphyrin-fullerene assemblies to realize the separation of charges.

Published on Jul 15, 2020in Chemical Science9.825
¡ DOI :10.1039/D0SC02028A
Maximilian Wolf4
Estimated H-index: 4
(International Council on Mining and Metals),
Dominik Lungerich14
Estimated H-index: 14
(University of Oxford)
+ 6 AuthorsDirk M. Guldi111
Estimated H-index: 111
(International Council on Mining and Metals)
Sources
Abstract
Here, we present a novel butadyine-linked HBC-ethynyl-porphyrin dimer, which exhibits in the ground state strong absorption cross sections throughout the UV and visible ranges of the solar spectrum. In short, a unidirectional flow of excited state energy from the HBC termini to the (metallo)porphyrin focal points enables concentrating light at the latter. Control over excitonic interactions within, for example, the electron donating porphyrin dimers was realized by complexation of bidentate ligands to set up panchromatic absorption that extends all the way into the near-infrared range. The bidentate binding motif was then exploited to create a supramolecular electron donor-acceptor assembly based on a HBC-ethynyl-porphyrin dimer and an electron accepting bis(aminoalkyl)-substituted fullerene. Of great relevance is the fact that charge separation from the photoexcited HBC-ethynyl-porphyrin dimer to the bis(aminoalkyl)-substituted fullerene is activated not only upon photoexciting the HBCs in the UV as well as the (metallo)porphyrins in the visible but also in the NIR. Implicit is the synergetic interplay of energy and charge transfer in a photosynthetic mimiking manner. The dimer and bis-HBC-ethynyl-porphyrin monomers, which serve as references, were probed by means of steady-state as well as time-resolved optical spectroscopies, including global target analyses of the time-resolved transient absorption data.
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References68
Newest
#1Max M. Martin (International Council on Mining and Metals)H-Index: 9
#2Dominik Lungerich (UTokyo: University of Tokyo)H-Index: 14
Last. Norbert Jux (International Council on Mining and Metals)H-Index: 31
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: Single-molecule electronic components (SMECs) are envisioned as next-generation building blocks in quantum circuit systems. However, challenges such as the reproducibility of the electrode attachment to the individual molecules hamper their fundamental investigation. For our purpose, we introduced quasi optoelectronic electrodes (QOEs) that allow for rapid investigations of the properties and suitability of compounds for molecular electronic devices. In particular, we probed hexa-peri-hexabenz...
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#1Wataru Suzuki (University of Tsukuba)H-Index: 5
#2Hiroaki Kotani (University of Tsukuba)H-Index: 16
Last. Takahiko Kojima (University of Tsukuba)H-Index: 40
view all 9 authors...
We have successfully constructed hydrogen-bonded supramolecular assemblies based on a diprotonated saddle-distorted porphyrin (H4DPP2+) and redox-active molecules bearing a carboxylate group, such as a RuII polypyridyl complex (RuIICOO–) that can act as an electron donor and a benzyl viologen derivative (BV2+COO–) that can act as an electron acceptor. Formation of supramolecular assemblies of H4DPP2+ with RuIICOO– (H4DPP2+(RuIICOO–)2 and H4DPP2+(RuIICOO–)(Cl–)) and BV2+COO– (H4DPP2+(BV2+COO–)2) ...
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#1Bart Limburg (University of Oxford)H-Index: 12
#2James O. Thomas (University of Oxford)H-Index: 8
Last. Harry L. Anderson (University of Oxford)H-Index: 91
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The effectiveness of five different anchor groups for non‐covalent interfacing to graphene electrodes are compared. A family of six molecules is tested in single‐molecule junctions: five consist of the same porphyrin core with different anchor groups, and the sixth is a reference molecule without anchor groups. The junction formation probability (JFP) has a strong dependence on the anchor group. Larger anchors give higher binding energies to the graphene surface, correlating with higher JFPs. Th...
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#1Dominik Lungerich (UTokyo: University of Tokyo)H-Index: 14
Last. Norbert Jux (International Council on Mining and Metals)H-Index: 31
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: A systematic series of superbenzene-porphyrin conjugates was synthesized and characterized. All conjugates show a high degree of cluster formation that correlates to the amount of tert-butylated hexa-peri-hexabenzocoronenes (tBuHBCs) attached to the porphyrin's periphery. Determined by mass spectrometry and X-ray diffraction, van der Waals (vdW) interactions like London dispersions (LD), stemming from solubilizing tert-butyl groups, were identified to be the major reason for the cluster format...
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#1Maximilian Wolf (International Council on Mining and Metals)H-Index: 4
#2Carmen Villegas (Complutense University of Madrid)H-Index: 8
Last. Dirk M. Guldi (International Council on Mining and Metals)H-Index: 111
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We report the synthesis of a full-fledged family of covalent electron donor–acceptor1–acceptor2 conjugates and their charge-transfer characterization by means of advanced photophysical assays. By virtue of variable excited state energies and electron donor strengths, either Zn(II)Porphyrins or Zn(II)Phthalocyanines were linked to different electron-transport chains featuring pairs of electron accepting fullerenes, that is, C60 and C70. In this way, a fine-tuned redox gradient is established to p...
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#1Johannes Holzwarth (FAU: University of Erlangen-Nuremberg)H-Index: 4
#2Konstantin Amsharov (FAU: University of Erlangen-Nuremberg)H-Index: 24
Last. Andreas Hirsch (FAU: University of Erlangen-Nuremberg)H-Index: 104
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In this article, we have successfully employed hexa-peri-hexabenzocoronides (HBC) as a model system for investigating the complex mechanism of the reductive functionalization of graphene. The well-defined molecular HBC system enabled us to gain deeper insights into the mechanism of the alkylation of reductively activated nanographenes. The separation and complete characterization of alkylation products clearly demonstrates that nanographene functionalization proceeds with exceptionally high regi...
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Porphyrin arrays consisting of three peripheral Zinc porphyrins (ZnPs) and a central free base porphyrin (H2P)—all rigidly linked to each other—serve as light-harvesting antennas as well as electron donors and are flexibly coupled to an electron-accepting C60 to realize the unidirectional flow of (i) excited-state energy from the ZnPs at the periphery to the H2P, (ii) electrons to C60, and (iii) holes to H2P and, subsequently, to ZnP. Dynamics following photoexcitation are elucidated by time-res...
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#1Martin D. Peeks (University of Oxford)H-Index: 14
#2Claudia E. Tait (University of Oxford)H-Index: 12
Last. Harry L. Anderson (University of Oxford)H-Index: 91
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The radical cations of a family of π-conjugated porphyrin arrays have been investigated: linear chains of N = 1–6 porphyrins, a 6-porphyrin nanoring and a 12-porphyrin nanotube. The radical cations were generated in solution by chemical and electrochemical oxidation, and probed by vis–NIR–IR and EPR spectroscopies. The cations exhibit strong NIR bands at ∼1000 nm and 2000–5000 nm, which shift to longer wavelength with increasing oligomer length. Analysis of the NIR and IR spectra indicates that ...
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#1Dominik Lungerich (FAU: University of Erlangen-Nuremberg)H-Index: 14
#2Jakob F. Hitzenberger (FAU: University of Erlangen-Nuremberg)H-Index: 7
Last. Norbert Jux (FAU: University of Erlangen-Nuremberg)H-Index: 31
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A feasible two-step synthesis and characterization of a full series of hexaarylbenzene (HAB) substituted (benzo)porphyrins is presented. Key steps represent the microwave-assisted porphyrin condensation and the statistical Diels-Alder reaction to the desired HAB-porphyrins. Regarding their applications, they proved to be easily accessible and effective high molecular mass calibrants for (MA)LDI mass spectrometry. The free-base and zinc(II) porphyrin systems, as well as the respective tetrabenzop...
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#1Ali Maghsoumi (Polytechnic University of Milan)H-Index: 6
#2Akimitsu Narita (MPG: Max Planck Society)H-Index: 46
Last. Matteo Tommasini (Polytechnic University of Milan)H-Index: 35
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We investigate the molecular structure and vibrational properties of perchlorinated hexa-peri-hexabenzocoronene (HBC-Cl) by density functional theory (DFT) calculations and IR and Raman spectroscopy, in comparison to the parent HBC. The theoretical and experimental IR and Raman spectra demonstrated very good agreement, elucidating a number of vibrational modes corresponding to the observed peaks. Compared with the parent HBC, the edge chlorination significantly alters the planarity of the molecu...
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Cited By3
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#1Philipp Haines (FAU: University of Erlangen-Nuremberg)H-Index: 9
#2Ramandeep Kaur (FAU: University of Erlangen-Nuremberg)H-Index: 6
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#1Alejandro Cadranel (UBA: University of Buenos Aires)H-Index: 13
#2Philipp Haines (FAU: University of Erlangen-Nuremberg)H-Index: 9
Last. Dirk M. Guldi (FAU: University of Erlangen-Nuremberg)H-Index: 111
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#1Michael Ruppel (International Council on Mining and Metals)H-Index: 4
#2Lampros‐Pascal Gazetas (FAU: University of Erlangen-Nuremberg)H-Index: 2
Last. Norbert Jux (FAU: University of Erlangen-Nuremberg)H-Index: 31
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Porphyrin‐based architectures have emerged as excellent candidates for artificial light‐harvesting antennae. Although tetrabenzoporphyrins (TBPs), the π‐extended “bigger brothers” of porphyrins, benefit from increased absorptivity in the near‐infrared (NIR), their utilization in light‐harvesting systems is still in its infancy. Within this work, we prepared two donor‐acceptor hetero dyads consisting of hexa‐peri‐hexabenzocoronenes (HBCs) to harvest high energetic near‐UV light, and a TBP core, w...
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