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采用[7]螺旋烯作为分子扳手的螺旋扭曲纳米带立体选择性环化π-扩展反应。

Helically twisted nanoribbons stereospecific annulative π-extension reaction employing [7]helicene as a molecular wrench.

作者信息

Swain Asim, Radacki Krzysztof, Braunschweig Holger, Ravat Prince

机构信息

Julius-Maximilians-Universität Würzburg, Institut für Organische Chemie Am Hubland 97074 Würzburg Germany

Julius-Maximilians-Universität Würzburg, Institut für Anorganische Chemie Am Hubland 97074 Würzburg Germany.

出版信息

Chem Sci. 2024 May 23;15(30):11737-11747. doi: 10.1039/d4sc01814a. eCollection 2024 Jul 31.

Abstract

Over the past decade, significant progress has been made in synthesizing atomically precise carbon nanostructures, particularly graphene nanoribbons (NRs), employing advanced synthetic methodologies. Despite these advancements, achieving control over the stereochemistry of twisted NRs has proven to be a formidable challenge. This manuscript presents a strategic approach to achieve absolute control over the single-handed helical conformation in a cove-edged NR. This strategy leverages enantiopure helicenes as a molecular wrench, intricately influencing the overall conformation of the NR. [7]helicenes stitched to the terminal K-regions of a conjugated pyrene NR through a stereospecific annulative π-extension reaction to produce a helically twisted NR with an end-to-end twist of 171°. Furthermore, a detailed investigation of the impact of twisting on the conformational population was studied by quantum chemical calculations.

摘要

在过去十年中,利用先进的合成方法在合成原子精确的碳纳米结构,特别是石墨烯纳米带(NRs)方面取得了重大进展。尽管有这些进展,但事实证明,控制扭曲NRs的立体化学是一项艰巨的挑战。本手稿提出了一种战略方法,以实现对凹边NR中单手螺旋构象的绝对控制。该策略利用对映体纯的螺旋烯作为分子扳手,复杂地影响NR的整体构象。通过立体特异性环化π-扩展反应,将[7]螺旋烯缝合到共轭芘NR的末端K区域,以产生具有171°端到端扭曲的螺旋扭曲NR。此外,通过量子化学计算详细研究了扭曲对构象群体的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1a14/11290328/e9beebd56e1c/d4sc01814a-f1.jpg

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