On the photophysics of nanographenes – investigation of functionalized hexa-<i>peri</i>-hexabenzocoronenes as model systems

Haines, Philipp; Reger, David; Träg, Johannes; Strauß, Volker; Lungerich, Dominik; Zahn, Dirk; Jux, Norbert; Guldi, Dirk M.

doi:10.1039/d0nr06802k

Cited by 13 publications

(14 citation statements)

References 43 publications

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“…Still, we assign it to an HBC-centered fluorescence. Responsible is the regioisomeric substitution pattern, by which the ZnPs and C 60 s are placed at the HBC, as it causes an effective symmetry-lowering . The change to polar benzonitrile results in an overall similar fluorescence except that the C 60 fluorescence is absent (Figures S12–S14).…”

Section: Resultssupporting

confidence: 82%

“…Responsible is the regioisomeric substitution pattern, by which the ZnPs and C 60 s are placed at the HBC, as it causes an effective symmetry-lowering. 30 The change to polar benzonitrile results in an overall similar fluorescence except that the C 60 fluorescence is absent (Figures S12−S14). From the quantitative analysis of the HBC fluorescence, we conclude a unidirectional energy transfer from HBC either to ZnP or C 60 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Hexa- peri -hexabenzocoronenes (HBCs) have recently attracted increasing attention due to their unique optoelectronic properties and the possibilities to utilize/tune or functionalize them. Multiple publications document the properties of HBCs regarding photon and charge management, as well as electronic communication. − Noteworthy is the efficient coupling between HBCs and porphyrins. ,− In, e.g., multiporphyrinic HBC conjugates, the interporphyrinic communication was found to be mediated by the HBC backbone and the resulting geometry …”

Section: Introductionmentioning

confidence: 99%

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Probing Charge Management across the π-Systems of Nanographenes in Regioisomeric Electron Donor–Acceptor Architectures

et al. 2022

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Inspired by light-induced processes in nature to mimic the primary events in the photosynthetic reaction centers, novel functional materials combine electron donors and acceptors, i.e., (metallo)porphyrins (ZnP) and fullerenes (C60), respectively, with emerging materials, i.e., nanographenes. We utilized hexa-peri-hexabenzocoronene (HBC) due to its versatility regarding functionalization and physicochemical properties, to construct three regioisomeric ZnP-HBC-C60 conjugates, which foster geometrical diversity by arranging ZnP and C60 in ortho-, meta-, and para-positions to each other. The corresponding hexaarylbenzene (HAB) motifs, with an interrupted π-system, were also prepared. Transient absorption measurements disclosed the fast population of charge transfer as well as singlet and triplet charge-separated states. With the help of density functional theory (DFT) calculations, we further conceive the communication across the HBCs and HABs. This work reveals the impact of both the geometrical arrangement with respect to through-space versus through-bond interactions and the structural rigidity/flexibility on the charge management across the different π-systems.

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Section: Resultssupporting

confidence: 82%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Probing Charge Management across the π-Systems of Nanographenes in Regioisomeric Electron Donor–Acceptor Architectures

et al. 2022

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“…The possibility of finely tuning physico-chemical properties makes NGs extremely interesting also in view of applications in materials science. Indeed, a multitude of works on the design and characterization of NGs with controllable size [ 17 , 18 ], edge structure [ 19 , 20 ], nonplanarity [ 21 , 22 ] and functional groups [ 23 , 24 ] have been reported in recent literature. In particular, distorted NGs are lately attracting a special interest since their curved non-planar structure determines an increase in the solubility and processability in organic solvents [ 25 , 26 ] and prevents their aggregation through

interactions.…”

Section: Introductionmentioning

confidence: 99%

Atomically Precise Distorted Nanographenes: The Effect of Different Edge Functionalization on the Photophysical Properties down to the Femtosecond Scale

et al. 2023

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Nanographenes (NGs) have been attracting widespread interest since they combine peculiar properties of graphene with molecular features, such as bright visible photoluminescence. However, our understanding of the fundamental properties of NGs is still hampered by the high degree of heterogeneity usually characterizing most of these materials. In this context, NGs obtained by atomically precise synthesis routes represent optimal benchmarks to unambiguously relate their properties to well-defined structures. Here we investigate in deep detail the optical response of three curved hexa-peri-hexabenzocoronene (HBC) derivatives obtained by atomically precise synthesis routes. They are constituted by the same graphenic core, characterized by the presence of a heptagon ring determining a saddle distortion of their sp2 network, and differ from each other for slightly different edge functionalization. The quite similar structure allows for performing a direct comparison of their spectroscopic features, from steady-state down to the femtosecond scale, and precisely disentangling the role played by the different edge chemistry.

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“…The application possibilities listed above have been discussed in this review. Particular attention is paid to nanographenes, including functionalized and heteroatoms-doped ones, which preparation and new applications constitute a “hot topic” in science and technology [ 6 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 ]. Currently, only bottom-up methods, where nanographene is constructed from smaller entities by stepwise organic synthesis, allow the preparation of nanographenes, including functionalized and doped ones, with perfect control of shapes and sizes and, therefore, perfectly defined properties [ 2 , 5 , 6 , 11 , 12 ,…”

Section: Introductionmentioning

confidence: 99%

Diels–Alder Cycloaddition with CO, CO2, SO2, or N2 Extrusion: A Powerful Tool for Material Chemistry

et al. 2021

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Phenyl, naphthyl, polyarylphenyl, coronene, and other aromatic and polyaromatic moieties primarily influence the final materials’ properties. One of the synthetic tools used to implement (hetero)aromatic moieties into final structures is Diels–Alder cycloaddition (DAC), typically combined with Scholl dehydrocondensation. Substituted 2-pyranones, 1,1-dioxothiophenes, and, especially, 1,3-cyclopentadienones are valuable substrates for [4 + 2] cycloaddition, leading to multisubstituted derivatives of benzene, naphthalene, and other aromatics. Cycloadditions of dienes can be carried out with extrusion of carbon dioxide, carbon oxide, or sulphur dioxide. When pyranones, dioxothiophenes, or cyclopentadienones and DA cycloaddition are aided with acetylenes including masked ones, conjugated or isolated diynes, or polyynes and arynes, aromatic systems are obtained. This review covers the development and the current state of knowledge regarding thermal DA cycloaddition of dienes mentioned above and dienophiles leading to (hetero)aromatics via CO, CO2, or SO2 extrusion. Particular attention was paid to the role that introduced aromatic moieties play in designing molecular structures with expected properties. Undoubtedly, the DAC variants described in this review, combined with other modern synthetic tools, constitute a convenient and efficient way of obtaining functionalized nanomaterials, continually showing the potential to impact materials sciences and new technologies in the nearest future.

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On the photophysics of nanographenes – investigation of functionalized hexa-peri-hexabenzocoronenes as model systems

Abstract: In this study, the syntheses of edge-functionalized hexa-peri-hexabenzocoronene and investigations by steady-state and time-resolved photospectroscopic techniques, which are completed by electron density distribution calculations, are reported.

Cited by 13 publications

References 43 publications

Probing Charge Management across the π-Systems of Nanographenes in Regioisomeric Electron Donor–Acceptor Architectures

Probing Charge Management across the π-Systems of Nanographenes in Regioisomeric Electron Donor–Acceptor Architectures

Atomically Precise Distorted Nanographenes: The Effect of Different Edge Functionalization on the Photophysical Properties down to the Femtosecond Scale

Diels–Alder Cycloaddition with CO, CO2, SO2, or N2 Extrusion: A Powerful Tool for Material Chemistry

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