Calix[4]arene-based molecular photosensitizers for sustainable hydrogen production and other solar applications

Boldrini, Chiara Liliana; Manfredi, Norberto; Montini, Tiziano; Baldini, Laura; Abbotto, Alessandro; Fornasiero, Paolo

doi:10.1016/j.cogsc.2021.100534

Cited by 5 publications

(4 citation statements)

References 40 publications

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“…Previously, Kesters et al [13] and Gao et al [14] extensively reported on the research progress of porphyrins in OPVs in 2015 and 2020, respectively. Furthermore, starting from 2010, several comprehensive reviews have been published on the application of porphyrins, phthalocyanines, and calix [4]arene-based macrocyclic dyes in DSSCs [15][16][17][18]. In this review, we present the research progress on organic macrocycles in optoelectronic devices and discuss in detail the structure-property relationship between macrocycle structures and their device performance.…”

Section: Introductionmentioning

confidence: 99%

Structure–Property Relationship of Macrocycles in Organic Photoelectric Devices: A Comprehensive Review

et al. 2023

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Macrocycles have attracted significant attention from academia due to their various applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, and dye-sensitized solar cells. Despite the existence of reports on the application of macrocycles in organic optoelectronic devices, these reports are mainly limited to analyzing the structure–property relationship of a particular type of macrocyclic structure, and a systematic discussion on the structure–property is still lacking. Herein, we conducted a comprehensive analysis of a series of macrocycle structures to identify the key factors that affect the structure–property relationship between macrocycles and their optoelectronic device properties, including energy level structure, structural stability, film-forming property, skeleton rigidity, inherent pore structure, spatial hindrance, exclusion of perturbing end-effects, macrocycle size-dependent effects, and fullerene-like charge transport characteristics. These macrocycles exhibit thin-film and single-crystal hole mobility up to 10 and 26.8 cm2 V−1 s−1, respectively, as well as a unique macrocyclization-induced emission enhancement property. A clear understanding of the structure–property relationship between macrocycles and optoelectronic device performance, as well as the creation of novel macrocycle structures such as organic nanogridarenes, may pave the way for high-performance organic optoelectronic devices.

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Section: Introductionmentioning

confidence: 99%

Structure–Property Relationship of Macrocycles in Organic Photoelectric Devices: A Comprehensive Review

et al. 2023

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“…The macrocyclic cavity of calix[4]arenes is aromatic and is therefore capable of hosting guest molecules via π‐π and CH‐π interactions, [17] with high efficiency also in water [18] . The use of calix[4]arene for photovoltaics and water splitting is still scantly reported in the literature, and only few studies have been published [19] …”

Section: Introductionmentioning

confidence: 99%

“…[18] The use of calix[4]arene for photovoltaics and water splitting is still scantly reported in the literature, and only few studies have been published. [19] In this work, we report the first example of calixarene-based dye-catalyst supramolecular dyads for water splitting in DS-PECs. [20] In particular, we combine the valuable host-guest properties of calix [4]arenes with easy-to-synthesize metal-free organic dye-sensitizers to prepare supramolecular assemblies with commonly used WOC (Figure 2).…”

Section: Introductionmentioning

confidence: 99%

Calix[4]arene‐Based Sensitizers for Host‐Guest Supramolecular Dyads for Solar Energy Conversion in Photoelectrochemical Cells.

et al. 2022

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The photogeneration of electricity and solar fuels by solar irradiation in photoelectrochemical cells is one of the sectors with the highest growth potential in the decarbonised society. However, the use of different components, in particular photosensitizers and catalysts, can present problems of charge transfer efficiency at the interface, leading to lower final efficiencies. In this work we present novel integrated photosensitizer‐catalyst dyads based on robust and, at the same time, flexible host‐guest non‐covalent interactions through the use of calix[4]arene cavities. Current photogeneration in photoelectrochemical cells showed twice greater efficiency in the integrated calixarene‐based host‐guest dyads compared to the traditional architecture based on the separate photosensitizer‐catalyst pair. Molecular dynamics studies have shown that the enhanced performance originates from an optimization of the distances between the centres of the photosensitizer, catalyst and semiconductor involved in the charge transfer processes, thus allowing a higher final efficiency of the charge photogeneration process.

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“…However, due to the rather low lipophilicity of the macrocycles, insufficient for the formation of a stable core during polymerization, in addition to spherical nanoparticles, the formation of open-chain polymers was also found. Calixarenes, an established and well-known class of macrocycles [16][17][18], are very promising building blocks for creating such polymer systems. Hydrophobic and hydrophilic fragments, including those containing anchor groups for polymerization, can be easily introduced into their structure.…”

Section: Introductionmentioning

confidence: 99%

NHC Polymeric Particles Obtained by Self-Assembly and Click Approach of Calix[4]Arene Amphiphiles as Support for Catalytically Active Pd Nanoclusters

et al. 2021

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A new polymeric NHC carrier was synthesized by sequential supramolecular self-assembly and copper-catalyzed azide-alkyne cycloaddition (CuAAC) of amphiphilic imidazolium calix[4]arenes with octyl lipophilic fragments. Obtained polytriazole-imidazolium particles were found as monodisperse submicron particles, with the average diameter of 236 ± 34 nm and average molecular weight of 1380 ± 96 kDa. Successful CuAAC polymerization has been proved using IR spectroscopy and high-resolution ESI mass spectrometry. Polymeric particles, as well as aggregates made from precursor macrocycles, were decorated by Pd clusters (2 nm) for further catalytic investigations. Pd nanoclusters, supported on the polymeric surface, were found highly catalytically active in the model reduction of p-nitrophenol, giving reaction rates an order of magnitude higher compared to literature examples. The reaction was recycled using the same catalyst five times without any loss of activity.

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Calix[4]arene-based molecular photosensitizers for sustainable hydrogen production and other solar applications

Cited by 5 publications

References 40 publications

Structure–Property Relationship of Macrocycles in Organic Photoelectric Devices: A Comprehensive Review

Structure–Property Relationship of Macrocycles in Organic Photoelectric Devices: A Comprehensive Review

Calix[4]arene‐Based Sensitizers for Host‐Guest Supramolecular Dyads for Solar Energy Conversion in Photoelectrochemical Cells.

NHC Polymeric Particles Obtained by Self-Assembly and Click Approach of Calix[4]Arene Amphiphiles as Support for Catalytically Active Pd Nanoclusters

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