Synergy of Electrostatic and π-π Interactions in the Realization of Nanoscale Artificial Photosynthetic Model Systems

Published on Jul 11, 2020in Angewandte Chemie12.959
· DOI :10.1002/ANIE.202006014
Tomás Torres97
Estimated H-index: 97
(UAM: Autonomous University of Madrid),
Eduardo Anaya-Plaza8
Estimated H-index: 8
(UAM: Autonomous University of Madrid)
+ 9 AuthorsDirk M. Guldi113
Estimated H-index: 113
(FAU: University of Erlangen-Nuremberg)
Sources
Abstract
In the scientific race to build up photoactive electron donor-acceptor systems with increasing efficiencies, little is known about the interplay of their building blocks when integrated into supramolecular nanoscale arrays, particularly in aqueous environments. Here, we describe an aqueous donor-acceptor ensemble whose emergence as a nanoscale material renders it remarkably stable and efficient. We have focused on a tetracationic zinc phthalocyanine (ZnPc) featuring pyrenes, which shows an unprecedented mode of aggregation, driven by subtle cooperation between electrostatic and π-π interactions. Our studies demonstrate monocrystalline growth in solution and a symmetry-breaking intermolecular charge transfer between adjacent ZnPcs upon photoexcitation. Immobilizing a negatively charged fullerene (C 60 ) as electron acceptor onto the monocrystalline ZnPc assemblies was found to enhance the overall stability, and to suppress the energy-wasting charge recombination found in the absence of C 60 . Overall, the resulting artificial photosynthetic model system exhibits a high degree of preorganization, which facilitates efficient charge separation and subsequent charge transport.
📖 Papers frequently viewed together
17 Citations
370 Citations
2010
1 Citations
References48
Newest
#1Dilek K. Dogutan (Harvard University)H-Index: 15
#2Daniel G. Nocera (Harvard University)H-Index: 109
ConspectusSunlight is an abundant energy source for a sustainable society. Indeed, photosynthetic organisms harness solar radiation to build the world around us by synthesizing energy-rich compounds from water and CO2. However, numerous energy conversion bottlenecks in the natural system limits the overall efficiency of photosynthesis; the most efficient plants do not exceed solar storage efficiencies of 1%. Artificial photosynthetic solar-to-fuels cycles may occur at higher intrinsic efficienci...
60 CitationsSource
#1Brandon K. Rugg (NU: Northwestern University)H-Index: 8
#2Matthew D. Krzyaniak (NU: Northwestern University)H-Index: 20
Last. Michael R. Wasielewski (NU: Northwestern University)H-Index: 121
view all 6 authors...
Quantum teleportation transfers the quantum state of a system over an arbitrary distance from one location to another through the agency of quantum entanglement. Because quantum teleportation is essential to many aspects of quantum information science, it is important to establish this phenomenon in molecular systems whose structures and properties can be tailored by synthesis. Here, we demonstrate electron spin state teleportation in an ensemble of covalent organic donor–acceptor–stable radical...
38 CitationsSource
#1Eduardo Anaya-Plaza (Aalto University)H-Index: 8
#2Ana Isabel Aljarilla (UAM: Autonomous University of Madrid)H-Index: 1
Last. Mauri A. Kostiainen (Aalto University)H-Index: 36
view all 8 authors...
: The generation of highly reactive oxygen species (ROS) at room temperature for application in organic synthesis and wastewater treatment represents a great challenge of the current chemical industry. In fact, the development of biodegradable scaffolds to support ROS-generating active sites is an important prerequisite for the production of environmentally benign catalysts. Herein, the electrostatic cocrystallization of a cationic phthalocyanine (Pc) and negatively charged tobacco mosaic virus ...
11 CitationsSource
#1Maxence Urbani (UAM: Autonomous University of Madrid)H-Index: 13
#2Gema de la Torre (UAM: Autonomous University of Madrid)H-Index: 33
Last. Tomás Torres (UAM: Autonomous University of Madrid)H-Index: 97
view all 4 authors...
Organic–inorganic lead halide perovskite absorbers in combination with electron and hole transporting selective contacts result in power conversion efficiencies of over 23% under AM 1.5 sun conditions. The advantage of perovskite solar cells is their simple fabrication through solution-processing methods either in n-i-p or p-i-n configurations. Using TiO2 or SnO2 as an electron transporting layer, a compositionally engineered perovskite as an absorber layer, and Spiro-OMeTAD as a HTM, several gr...
86 CitationsSource
#1Matthias LehmannH-Index: 31
#2Moritz DechantH-Index: 4
Last. Christoph LambertH-Index: 56
view all 5 authors...
: Two shape-persistent star mesogens with oligo(phenylene ethenylene) arms and a phthalocyanine core-one providing free space (2) and one sterically encumbered by four fullerenes attached through spacers (3)-have been successfully synthesized. In contrast to the smaller discotic derivative 1, mesogen 2 forms a columnar liquid crystal (LC), which can only be partially aligned without π-stacking, while 3 is not an LC. Exceptionally, the 1:1 mixture of 2 and 3 forms an alignable columnar LC with st...
19 CitationsSource
#1Matthias LehmannH-Index: 31
#2Moritz DechantH-Index: 4
Last. Christoph LambertH-Index: 56
view all 5 authors...
2 CitationsSource
#1Yu-Min Liu (Ha Tai: Xiamen University)H-Index: 5
#2Hao Hou (Ha Tai: Xiamen University)H-Index: 4
Last. Klaus Müllen (MPG: Max Planck Society)H-Index: 181
view all 7 authors...
Conjugation of nanographenes (NGs) with electro-active molecules can establish donor-acceptor π-systems in which the former generally serve as the electron-donating moieties due to their electronic-rich nature. In contrast, here we report a series of reversed donor-acceptor structures are obtained by C–N coupling of electron-deficient perchlorinated NGs with electron-rich anilines. Selective amination at the vertexes of the NGs is unambiguously shown through X-ray crystallography. By varying the...
14 CitationsSource
#1Luis M. Arellano (UCLM: University of Castilla–La Mancha)H-Index: 6
#2Luis Martín-GomisH-Index: 17
Last. Fernando Langa (UCLM: University of Castilla–La Mancha)H-Index: 41
view all 10 authors...
Enriched semiconducting single-walled carbon nanotubes (SWCNT (6,5) and SWCNT (7,6)) and HiPco nanotubes were covalently functionalized with either zinc phthalocyanine or silicon phthalocyanine as electron donors. The synthetic strategy resulted in edge-on and face-on geometries with respect to the phthalocyanine geometry, with both phthalocyanines held by an electronically conducting diphenylacetylene linker. The extent of functionalization in the MPc-SWCNT (M = Zn or Si) donor–acceptor nanohyb...
12 CitationsSource
#1Maximilian Wolf (International Council on Mining and Metals)H-Index: 4
#2Carmen Villegas (Complutense University of Madrid)H-Index: 7
Last. Dirk M. Guldi (International Council on Mining and Metals)H-Index: 113
view all 8 authors...
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...
27 CitationsSource
#1Jing-Jing Li (NKU: Nankai University)H-Index: 8
#2Yong Chen (NKU: Nankai University)H-Index: 43
Last. Yu Liu (NKU: Nankai University)H-Index: 104
view all 5 authors...
An efficient artificial light-harvesting system is fabricated from a cyclic polysaccharide, sulfato-β-cyclodextrin (SCD); an aggregation-induced emission molecule, an oligo(phenylenevinylene) derivative (OPV-I); and a fluorescent dye, nile red (NiR), via noncovalent interactions in an aqueous solution. In this system, the OPV-I/SCD supramolecular assembly acts as a donor, and NiR that is loaded into the OPV-I/SCD assembly acts as an acceptor. Significantly, an efficient energy-transfer process o...
114 CitationsSource
Cited By3
Newest
#1Asma Rahali (Carthage University)H-Index: 1
#2Ahmed Shaukat (Aalto University)H-Index: 3
Last. Eduardo Anaya-Plaza (Aalto University)H-Index: 8
view all 8 authors...
Design and synthesis of novel photosensitizer architectures is a key step toward new multifunctional molecular materials. Photoactive Janus-type molecules provide interesting building blocks for such systems by presenting two well-defined chemical functionalities that can be utilized orthogonally. Herein a multifunctional phthalocyanine is reported, bearing a bulky and positively charged moiety that hinders their aggregation while providing the ability to adhere on DNA origami nanostructures via...
Source
#1Marie Halaskova (Charles University in Prague)H-Index: 1
#2Asma Rahali (UAM: Autonomous University of Madrid)H-Index: 1
Last. Petr Zimcik (Charles University in Prague)H-Index: 23
view all 10 authors...
Photodynamic therapy is a treatment modality of cancer based on the production of cytotoxic species upon the light activation of photosensitizers. Zinc phthalocyanine photosensitizers bearing four ...
2 CitationsSource
#1Giovanni Bottari (UAM: Autonomous University of Madrid)H-Index: 25
#2Gema de la Torre (UAM: Autonomous University of Madrid)H-Index: 33
Last. Tomás Torres (UAM: Autonomous University of Madrid)H-Index: 97
view all 4 authors...
Abstract This review highlights the combined effort of the Torres and Guldi groups in the preparation and study of porphyrinoid-based photo- and electro-active systems. The perfect synergy between the deep knowledge on the chemistry of porphyrinoids and advanced carbon allotropes possessed by the Spanish team, and the profound expertise in the advanced photophysical characterization and photon- and charge-management held by the German group represents the real asset of this transnational collabo...
4 CitationsSource