Azaacene Diradicals Based on Non-Kekulé Meta-Quinodimethane with Large Two-Photon Cross-Sections in the Infrared Spectral Region

被引：1

作者：

Fuchs, Kathleen ^{[1
]}

Oberhof, Nils ^{[2
]}

Sauter, Gabriel ^{[3
]}

Pollien, Audrey ^{[3
,4
]}

Broedner, Kerstin ^{[1
]}

Rominger, Frank ^{[1
]}

Freudenberg, Jan ^{[1
]}

Dreuw, Andreas ^{[2
]}

Tegeder, Petra ^{[3
]}

Bunz, Uwe H. F. ^{[1
]}

机构：

[1] Heidelberg Univ, Organ Chem Inst, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany

[2] Heidelberg Univ, Interdisciplinary Ctr Sci Comp, Im Neuenheimer Feld 205, D-69120 Heidelberg, Germany

[3] Heidelberg Univ, Phys Chem Inst, Im Neuenheimer Feld 253, D-69120 Heidelberg, Germany

[4] Univ Paris Saclay, Ecole Normale Super Paris Saclay, 4 Av Sci, F-91190 Gif sur Yvette, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2024年 / 63卷 / 48期

关键词：

aromaticity; azaacene; Clar sextets; non-Kekul & eacute; diradical; two-photon absorption; ORGANIC-SYNTHESIS; CRYSTAL-STRUCTURE; PORPHYRIN ARRAYS; ABSORPTION; AROMATICITY; HYDROCARBON; DELOCALIZATION; THERMOLYSIS; DERIVATIVES; MOLECULES;

D O I：

10.1002/anie.202406384

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Non-Kekul & eacute; quinoidal azaacences m-A (1 a,b) were synthesized and compared to their para- and ortho-quinodimethane analogues. m-A display high diradical characters (1 b: y0 = 0.88) due to their meta-quinodimethane (m-QDM) topology. Electron paramagnetic, nuclear magnetic resonance spectroscopies and supraquantum interference device measurements in combination with quantum-chemical calculations revealed singlet ground states for m-A with singlet-triplet gaps Delta EST (0.13-0.25 kcal mol-1) and thermally populated triplet states. These non-Kekul & eacute; structures are over all void of zwitterionic character and possess record high two-photon absorption cross sections over a broad spectral range in the near-infrared.

引用

页数：7

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