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. 2024 Dec 10;30(69):e202403250.
doi: 10.1002/chem.202403250. Epub 2024 Nov 16.

Manifold-Fused Porphyrin-Nanographene Conjugates

Christoph Oleszak  1 , Christian L Ritterhoff  2 , Max M Martin  1 , Bernd Meyer  2 , Norbert Jux  1
Affiliations

Manifold-Fused Porphyrin-Nanographene Conjugates

Christoph Oleszak et al. Chemistry. .

Abstract

A library of novel π-extended porphyrin-hexabenzocoronene (HBC) architectures is presented. Two distinct synthetic pathways were utilized to obtain either phenyl- or HBC-fused compounds. Absorption experiments reveal the species' exciting photophysical and optoelectronic properties. Depending on the degree of π-extension, the number of porphyrins, and their relative position, a decisive change in shape, panchromatic broadening, and red-shifting of the absorption curves is observed. Theoretical studies give more profound insight into the molecule's electronic structures, showing vast decreases in HOMO-LUMO energy gaps.

Keywords: Fusion reaction; Porphyrinoids; Post-functionalization; Scholl oxidation; π-Extension.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Recent advances in the field of HBC and porphyrin chemistry by the Jux group. a) Bis‐porphyrin‐HBC conjugates; b) Fused porphyrins.[ 33 , 34 ]
Scheme 1
Scheme 1
Design of a phenyl‐fused borylated porphyrin building block 5. Reagents and conditions: a) FeCl3 (8 equiv), CH3NO2, CH2Cl2, 24 h, 0 °C→rt; b) HBpin, PdCl2(PPh3)2, NEt3, 1,2‐DCE, 24 h, 90 °C.
Scheme 2
Scheme 2
Synthesis of multiple phenyl‐fused nickel‐porphyrin‐HBC conjugates via Suzuki cross‐coupling. Reagents and conditions: c) Pd(PPh3)4, Cs2CO3, toluene, DMF, 18 h, 80 °C. Ar=mesityl.
Scheme 3
Scheme 3
Synthesis of nickel‐porphyrin‐HBC conjugates via Suzuki cross‐coupling. Reagents and conditions: c) Pd(PPh3)4, Cs2CO3, toluene, DMF, 18 h, 80 °C. Ar=mesityl.
Scheme 4
Scheme 4
Reagents and conditions: FeCl3 (60 equiv), CH3NO2, CH2Cl2; b) 24 h, 0 °C→rt; c) 72 h, 0 °C→rt; d) 148 h, 0 °C→rt. Ar=mesityl.
Scheme 5
Scheme 5
Synthesis of triple‐fused porphyrin‐HBC tri ‐HBC. Reagents and conditions: e) FeCl3 (60 equiv), CH3NO2, CH2Cl2, 72 h, 0 °C→rt. Ar=mesityl.
Figure 2
Figure 2
UV/Vis spectra of o ‐Ph, m ‐Ph, p ‐Ph, and tri ‐Ph (CH2Cl2).
Figure 3
Figure 3
UV/Vis spectra of o ‐HBC, m ‐HBC, p ‐HBC, and tri ‐HBC (CH2Cl2).
Figure 4
Figure 4
DFT‐optimized structures of a) o ‐Ph, m ‐Ph, p ‐Ph, and tri ‐Ph; b) o ‐HBC, m ‐HBC, p ‐HBC, and tri ‐HBC.
Figure 5
Figure 5
Calculated (yellow) and experimental (purple) UV/Vis absorption spectra of o ‐HBC, m ‐HBC, p ‐HBC, and tri ‐HBC (CH2Cl2). The TD‐DFT calculations were done with the B3LYP hybrid functional. Solvation effects were included by a continuum polarization model.
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