Engineering the HOMO–LUMO gap of indeno[1,2-<i>b</i>]fluorene

Casares, Raquel; Martínez-Pinel, Álvaro; Rodríguez‐González, Sandra; Márquez, Irene R.; Lezama, Luís; González, M. Teresa; Leary, Edmund; Blanco, Víctor Francisco Sampedro; Fallaque, Joel G.; Dı́az, Cristina; Martín, Fernando; Cuerva, Juan M.; Millán, Alba

doi:10.1039/d2tc02475f

Cited by 26 publications

(19 citation statements)

References 44 publications

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“…An intuitive interpretation is that the smaller HOMO–LUMO gap of Ce 2 O@C 88 can result in a larger conductance. 38,40,41 In addition, the experimental conductance of Ce 2 O@C 88 is 1.6 times higher than that of C 60 . This reveals the significant research value of the electron transportation properties of metallofullerenes.…”

Section: Resultsmentioning

confidence: 95%

Structure and single-molecule conductance of two endohedral metallofullerenes with large C₈₈cage

Wang

Liu

et al. 2023

Nanoscale

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Section: Resultsmentioning

confidence: 95%

Structure and single-molecule conductance of two endohedral metallofullerenes with large C₈₈cage

Wang

Liu

et al. 2023

Nanoscale

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“…[25] Molecular structures were fully optimized without imposing symmetry constraints by DFT computations at the B3LYP/aug-cc-pVTZ level. [26] The good performance of the B3LYP functional in benchmark studies justifies its extensive use and several recent reports confirm its reliability in aromaticity related applications on ground and excited states (see for example References [2,3,5,6,10,11,15,16,21,24] and references therein). The restricted and unrestricted procedures were applied for singlet and triplet electronic states respectively.…”

Section: Computational Methodologymentioning

confidence: 99%

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ

Borosky,

Laali

2023

ChemistrySelect

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Dications and dianions derived from fused PAHs and hetero‐PAHs were investigated by means of DFT calculations. The electronic, energetic, and structural features of the singlet and triplet electronic states of these doubly charged species were computationally determined and compared with those of the corresponding neutral parent aromatic and heteroaromatic compounds. The aromatic, nonaromatic or antiaromatic character of the studied diions was evaluated via magnetic criteria, namely NICS and 1H NMR chemical shifts, and by the HOMA structural index. Linear correlations were revealed between the computed HOMO‐LUMO gaps and the magnetic parameters which could serve as a guiding tool in the modulation of molecular properties, and for designing new materials derived from this type of compounds.

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“…Additionally, the [2,1- c ]IF scaffold was known 1 but its charge-carrier mobility was unknown, and it was speculated to have poor performance due to its U-shape hindering π–π stacks. 2e Inspired by the reports of ambipolar charge transport of [1,2- b ]IF 2f with symmetrical disubstitution, and use of [1,2- b ]IF for single-molecule conductance studies, 2h herein, we report the syntheses of four unsymmetrical [2,1- c ]IFs 7 – 10 and one symmetrical [2,1- c ]IF 17 including their characterization by both experimental and computational 15 approaches, and the charge-carrier mobilities of 1 , 7 , 8 and 17 were experimentally investigated using the space charge limited current (SCLC) method.…”

Section: Introductionmentioning

confidence: 99%

Exploring Indeno[2,1-c]fluorene Antiaromatics with Unsymmetrical Disubstitution and Balanced Ambipolar Charge-Transport Properties

et al. 2023

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Unsymmetrically disubstituted antiaromatic indenofluorene (IF), in comparison to aromatic pentacene counterpart with unsymmetrical disubstitution, was rare in literature until our recent report on indeno[1,2-b]fluorene and indeno[2,1-a]fluorene. Described herein is straightforward access to unsymmetrically disubstituted indeno[2,1-c]fluorenes bearing mesityl at one apical carbon and C6F5, 3,5-(CF3)2C6H3, and CCSii-Pr3 at the other apical carbon, including 4-methoxyphenyl/3,5-(CF3)2C6H3 push/pull substitution at the apical carbons with appreciable orbital density and a previously unknown symmetrically C6F5-disubstituted [2,1-c]IF. The electronic properties of the unsymmetrical derivatives lie halfway in between the two symmetrical counterparts, while the 4-methoxyphenyl derivative showed the smallest HOMO-LUMO energy gap and near-infrared absorption with intramolecular charge transfer character. Single-crystal analyses showed 1D-columnar stacks for the unsymmetrical motif with the C6F5 units co-facially π-stacked with the IF core, whereas symmetrically C6F5-disubstituted [2,1-c]IF, with a low-lying LUMO, showed intermolecular π-π stacks between the IFs core that resulted in good electron mobility (μe = 8.66 × 10−3 cm2 V−1 s−1) under space charge limited current measurements. Importantly, balanced ambipolar charge-transport behaviour could be extracted for an IF series with symmetrical/unsymmetrical substitutions, in comparison to its π-contracted pentalene congener.

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Engineering the HOMO–LUMO gap of indeno[1,2-b]fluorene

Abstract: A direct, efficient and versatile strategy for modulation of optoelectronic and magnetic properties of indeno[1,2-b]fluorene has been developed. 4-substituted-2,6-dimethylphenyl acetylene groups placed in the apical carbon of the five-membered rings...

Cited by 26 publications

References 44 publications

Structure and single-molecule conductance of two endohedral metallofullerenes with large C₈₈cage

Structure and single-molecule conductance of two endohedral metallofullerenes with large C₈₈cage

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ

Exploring Indeno[2,1-c]fluorene Antiaromatics with Unsymmetrical Disubstitution and Balanced Ambipolar Charge-Transport Properties

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Engineering the HOMO–LUMO gap of indeno[1,2-b]fluorene

Abstract: A direct, efficient and versatile strategy for modulation of optoelectronic and magnetic properties of indeno[1,2-b]fluorene has been developed. 4-substituted-2,6-dimethylphenyl acetylene groups placed in the apical carbon of the five-membered rings...

Cited by 26 publications

References 44 publications

Structure and single-molecule conductance of two endohedral metallofullerenes with large C88cage

Structure and single-molecule conductance of two endohedral metallofullerenes with large C88cage

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compoundsǂ

Exploring Indeno[2,1-c]fluorene Antiaromatics with Unsymmetrical Disubstitution and Balanced Ambipolar Charge-Transport Properties

Contact Info

Product

Resources

About

Structure and single-molecule conductance of two endohedral metallofullerenes with large C₈₈cage

Structure and single-molecule conductance of two endohedral metallofullerenes with large C₈₈cage

Gauging the Aromatic, Antiaromatic, and Nonaromatic Character of the Dications and Dianions Derived from Fused Carbocyclic and Heterocyclic Compounds^ǂ