Pentaindenocorannulene: Properties, Assemblies, and C<sub>60</sub> Complex

Lampart, Samuel; Roch, Loı̈c M.; Dutta, Amit Kumar; Wang, Yujia; Warshamanage, Rangana; Finke, Aaron D.; Linden, Anthony; Baldridge, Kim K.; Siegel, Jay S.

doi:10.1002/anie.201608337

Cited by 51 publications

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“…More importantly, bowl curvature is seen to be an effective control element for packing in the solid state. For example, in a designed class of indeno‐substituted derivatives, it was discovered that the number and arrangement of indeno substituents on the corannulene core governs the resulting bowl orientation within 1D columnar stacks . This type of system enables the potential for tuning the character of charge‐transfer excitations along molecular columns.…”

Section: Introductionmentioning

confidence: 99%

“…The aforementioned class of indeno‐substituted curved aromatics serves well to illustrate these points. In our recent efforts, use of G 0 W 0 ‐BSE approaches enabled access to excitonic properties in the crystal for the curved aromatic bowl structures, diindenocorannulene ( 3 ), and one polymorph of pentaindenocorannulene ( 5 ), synthesized by our experimental collaborators . The disubstituted indeno form, 3 , is observed to crystallize in a monoclinic space group with molecular bowls aligned into 1D parallel columns, with a staggered orientation of the indeno‐groups (Figure A) .…”

Section: Introductionmentioning

confidence: 99%

“…The disubstituted indeno form, 3 , is observed to crystallize in a monoclinic space group with molecular bowls aligned into 1D parallel columns, with a staggered orientation of the indeno‐groups (Figure A) . In the most recent polymorph of 5 , the molecular units stack into infinite bowl‐in‐bowl columns, with opposite orientation of the bowl opening between neighboring stacks (Figure B) …”

Section: Introductionmentioning

confidence: 99%

“…In analogy to C 50 H 10, one finds interesting the results of structural modification on SAMO properties with the previously mentioned pentaindenocorannulene, 5 , structure. Such structural diversification enables self‐aggregation as well as complexation with fullerene, which manifest important variation in SAMOs properties. Detailed G 0 W 0 theoretical analysis on the isolated molecule, 5 , and its complex with C 60 , 5 @C 60 , was carried out to more fully understand these properties.…”

Section: Introductionmentioning

confidence: 99%

“…In particular, the interest lies in the potential of this material to enable electron transport through SAMO hybridization between the component fragments in the 5 @C 60 complex. In the latter complex, fullerene is shown to fit ideally into the concave surface of the 5 molecule …”

Section: Introductionmentioning

confidence: 99%

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From charge‐transfer excitations to charge‐transport phenomena in organic molecular crystals

Zoppi

Baldridge

2017

Int J of Quantum Chemistry

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Functional devices based on properties inherent in single organic molecules offer promise for use in technological applications, particularly building blocks that can take on diverse electronic functions with tuning through chemical design and synthesis. Morphological features of curved aromatic structures offer exploration into a wealth of phenomenology as a function of environment, such as exemplified for super atomic molecular orbitals. This review discusses current stateof-the-art electronic structure approaches for prediction of structural, electronic, optical, and transport properties of planar and curved designed components. Important principle for design lies in understanding and control of the solid-state packing and intermolecular interactions of individual building block units, for which many body perturbation techniques are essential. Molecular and solid state engineering is shown to be effective toward tailoring new materials with optimal transport properties, with valuable insight provided by high level computational prediction.charge transfer, charge transport, curved aromatics, GW-BSE theory, SAMO | I N TR ODU C TI ONSome of the most relevant problems in the field of condensed matter, nanoscience, and renewable energy applications are related to the discovery and understanding of complex materials engineered to meet a specific functionality. [1][2][3] Renewed interest in the use of conjugated molecules with delocalized p electrons as key components in nanoscale electronics and optoelectronic devices has motivated recent abilities to construct singlemolecule junctions and measure their transport properties. [4][5][6] As conductor dimensions approach the nanoscale, design principles turn toward creation of molecules with tunable functionality to enable control of charge transport on the molecular scale. [5,7] Organic-organic (hybrid) interfaces are primary components in emerging technologies, such as organic and molecular electronics [8] and photovoltaic cells.[9] These complex systems can often strongly influence the electrical and optical characteristics of a specific structure or device.[10] Key material properties, such as the level alignment at functional interfaces, [11,12] the ability of charge carriers to be injected into a conductive substrate, the efficiency of optical excitations to split into free carriers, [13] and so on, poorly described within standard density functional theory (DFT) methodologies, [14] are ultimately factors in determining unique electronic properties of a given complex. As such, pressing needs have emerged for improved understanding of the details involved in optimization and control of electronic transport phenomena in aromatic systems, two key representative components of which constitutes the focus of the present work.I. The conventional mechanism for charge transport in conjugated materials involves the overlap of delocalized p molecular orbitals, which extend through a plane and can facilitate transport. Directed confinement of electronic states in one...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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From charge‐transfer excitations to charge‐transport phenomena in organic molecular crystals

Zoppi

Baldridge

2017

Int J of Quantum Chemistry

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Bowl on the ring: Molecular crowns hosting fullerenes synergistically by buckybowl and nanohoop

Song,

Liu,

Hua

et al. 2024

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Curved π‐electron systems show unique properties and assembly feature that enable the specific applications in materials science and supramolecular chemistry. Herein, fullerene, carbon nanohoop and π‐bowl are integrated by the coupling of covalent and supramolecular tactics. Firstly, π‐bowl trichalcogenasumanenes (TCSs) are fused with a carbon nanohoop [10]CPP via covalent joint to form molecular crowns 4a/4b, which show structural and electronic complementarity and accordingly strong binding affinity to C60/C70. Secondly, the supramolecular assemblies of 4a/4b with fullerenes afford the host‐guest complexes 4a/4b⊃C60/C70 in solution (molar ratio, 2:1) and solid state (molar ratio, 1:1). In the crystals of host–guest complexes, the intra‐cluster and inter‐cluster interactions are respectively dominated by the [10]CPP and TCSs moieties of 4a/4b. Additionally, it is found that 4a/4b are good photosensitizers for generating 1O2 and show structural adaptability in accordance to assembly conditions. 4a/4b take an endo‐conformation in their own crystals with TCSs and [10]CPP moieties being bowl‐shaped and elliptical, respectively. In contrast, the [10]CPP on 4a/4b changes into circular and the TCSs moiety becomes flat (for 4b) or shows bowl inversion to be exo‐conformation (for 4a) in 4a/4b⊃C60/C70.

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Hierarchical Corannulene‐Based Materials: Energy Transfer and Solid‐State Photophysics

et al. 2017

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Abstract:We report the first example of ad onor-acceptor corannulene-containing hybrid material with rapid ligand-toligand energy transfer (ET). Additionally,weprovide the first time-resolved photoluminescence (PL) data for any corannulene-based compounds in the solid state.C omprehensive analysis of PL data in combination with theoretical calculations of donor-acceptor exciton coupling was employed to estimate ET rate and efficiency in the prepared material. The ligand-to-ligand ET rate calculated using two models is comparable with that observed in fullerene-containing materials,w hich are generally considered for molecular electronics development. Thus,the presented studies not only demonstrate the possibility of merging the intrinsic properties of p-bowls, specifically corannulene derivatives,w ith the versatility of crystalline hybrid scaffolds,b ut could also foreshadowt he engineering of anovel class of hierarchicalcorannulene-based hybrid materials for optoelectronic devices.While the compromise between strain and aromaticity is ap ersistent synthetic challenge, [1][2][3] the bowl shape and electronic properties of corannulene derivatives (buckybowls, Scheme 1) imply an unrevealed potential for molecular electronics development similar to their close famous analogues,fullerenes.The main success of the latter in the field of optoelectronics is associated with very fast energy/electron transfer, which has been demonstrated in numerous photophysical studies. [4][5][6] In contrast, development of buckybowlcontaining materials with desirable properties is still in its infancy. Fori nstance,d uring the 50 years since the discovery of the first solution route for corannulene preparation (1966), [1] only around 20 papers [2, include any photophysical studies,d espite nearly 1000 publications focused on corannulene.T othe best of our knowledge,there are only two reports [8,10] in the area of corannulene solid-state photophysics.F urthermore,n os olid-state time-resolved photoluminescence (PL) data or energy transfer (ET) studies have been reported for any corannulene-containing compounds despite the fact that ET rate and efficiency are crucial fundamental parameters for applications ranging from organic photovoltaics to photocatalysis. [33,34] This gap in material development was the major driving force to initiate the presented study,especially taking into account the recent progress in corannulene chemistry. [35] Our shift from more traditional flat aromatic hydrocarbons [36] towards p-bowls (for example,c orannulene) was also driven by 1) their significant dipole moment, 2) the possibility to extend the dimensionality of 3D hybrid frameworks through the p-bowl curvature,3 )potential for charge stabilization on the surface owing to doubly degenerate lowest unoccupied molecular orbitals (LUMOs), 4) anticipated effective intermolecular charge transport, and 5) presence of theoretically predicted super atomic molecular orbitals,w hich are key factors for intermolecular charge/ energy transport distinct from the c...

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Pentaindenocorannulene: Properties, Assemblies, and C₆₀ Complex

Abstract: Pentaindenocorannulene (C H , 1), a deep bowl polynuclear aromatic hydrocarbon, accepts 4 electrons, crystallizes in columnar bowl-in-bowl assemblies and forms a nested C @1 complex. Spectra, structures and computations are presented.

Cited by 51 publications

References 55 publications

From charge‐transfer excitations to charge‐transport phenomena in organic molecular crystals

From charge‐transfer excitations to charge‐transport phenomena in organic molecular crystals

Bowl on the ring: Molecular crowns hosting fullerenes synergistically by buckybowl and nanohoop

Hierarchical Corannulene‐Based Materials: Energy Transfer and Solid‐State Photophysics

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Pentaindenocorannulene: Properties, Assemblies, and C60 Complex

Abstract: Pentaindenocorannulene (C H , 1), a deep bowl polynuclear aromatic hydrocarbon, accepts 4 electrons, crystallizes in columnar bowl-in-bowl assemblies and forms a nested C @1 complex. Spectra, structures and computations are presented.

Cited by 51 publications

References 55 publications

From charge‐transfer excitations to charge‐transport phenomena in organic molecular crystals

From charge‐transfer excitations to charge‐transport phenomena in organic molecular crystals

Bowl on the ring: Molecular crowns hosting fullerenes synergistically by buckybowl and nanohoop

Hierarchical Corannulene‐Based Materials: Energy Transfer and Solid‐State Photophysics

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Product

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Pentaindenocorannulene: Properties, Assemblies, and C₆₀ Complex