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基于薁的螺旋烯中的基态和激发态芳香性

Ground and Excited State Aromaticity in Azulene-Based Helicenes.

作者信息

Reyes Amisadai Lorenzo, Ndiaye Fatim Ndeye, Artigas Albert, Coquerel Yoann, Terrioux Cyril, Prcovic Nicolas, Hagebaum-Reignier Denis, Carissan Yannick

机构信息

Aix Marseille Univ, CNRS, Centrale Med, iSm2, Marseille, France.

Facultat de Ciències, Universitat de Girona, Campus Montilivi, Carrer de Maria Aurèlia Capmany i Farnès 69, 17003, Girona, Catalunya, Spain.

出版信息

Chemphyschem. 2025 Apr 1;26(7):e202400833. doi: 10.1002/cphc.202400833. Epub 2025 Mar 4.

DOI:10.1002/cphc.202400833
PMID:39831429
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11963990/
Abstract

Electron delocalization is studied in the ground singlet and first excited triplet states of azulene-containing helicenes. After showing that the compounds we study can be synthesized, we show that they exhibit a charge separation in the ground state, which does not appear in their triplet excited state. Then, magnetically induced properties (IMS3D and ACID) and electron density decomposition methods (EDDB) are used to rationalize aromaticity in these systems. For azulene-based helicenes larger than a critical size, that is, for more than six fused cycles, unexpected aromatic delocalization circuits appear. This feature is understood via the decomposition of the wavefunction on sets of carefully chosen local electronic structures and fragment orbital diagrams.

摘要

对含薁并苯的螺旋烯的基态单重态和第一激发三重态中的电子离域进行了研究。在证明我们所研究的化合物可以合成之后，我们表明它们在基态表现出电荷分离，而在三重激发态中则不会出现这种情况。然后，利用磁诱导性质（IMS3D和ACID）以及电子密度分解方法（EDDB）来解释这些体系中的芳香性。对于大于临界尺寸的基于薁的螺旋烯，即对于超过六个稠合环的情况，会出现意想不到的芳香离域回路。通过在精心选择的局部电子结构和片段轨道图上对波函数进行分解，可以理解这一特征。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/73252f4bc6db/CPHC-26-e202400833-g001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/76a1d3b63c09/CPHC-26-e202400833-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/73252f4bc6db/CPHC-26-e202400833-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/0cf9a418eb10/CPHC-26-e202400833-g016.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/3cb2c5a4d2b4/CPHC-26-e202400833-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/0e89a8ff6844/CPHC-26-e202400833-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/d8fa17ece466/CPHC-26-e202400833-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/f3f052bf5e20/CPHC-26-e202400833-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/52e621c400c4/CPHC-26-e202400833-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/908aa7df6924/CPHC-26-e202400833-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/8d3f39e7d04e/CPHC-26-e202400833-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/8d83fcd513af/CPHC-26-e202400833-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/ff85caea96e1/CPHC-26-e202400833-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/5e6b95ea73ce/CPHC-26-e202400833-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/582ccf99837a/CPHC-26-e202400833-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/6e667abade1d/CPHC-26-e202400833-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/85006a027cf1/CPHC-26-e202400833-g017.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/76a1d3b63c09/CPHC-26-e202400833-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ceed/11963990/73252f4bc6db/CPHC-26-e202400833-g001.jpg

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本文引用的文献

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Aromaticity in Semi-Condensed Figure-Eight Molecules.半缩合数字8分子中的芳香性
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Is azulene's local aromaticity and relative stability driven by the Glidewell-Lloyd rule?
薁的局域芳香性和相对稳定性是由格莱德韦尔-劳埃德规则驱动的吗？
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Helicene Aromaticity Deviates from the Clar Rule-On the Electronic Dissimilarity of Large Isomeric Fibonacenes.螺旋烯芳香性偏离克拉尔规则——关于大型同分异构斐波那契烯的电子差异
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Helical Nanographenes Bearing Pentagon-Heptagon Pairs by Stepwise Dehydrocyclization.通过逐步脱氢环化生成的带有五角形 - 七角形对的螺旋纳米石墨烯。
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π-Extended Helical Multilayer Nanographenes with Layer-Dependent Chiroptical Properties.具有层依赖手性光学性质的π-扩展螺旋多层纳米石墨烯
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