Controlling the Chiroptical Properties of Pyrene-Based Tweezers by Conformation Locking

IF 3 4区化学 Q3 CHEMISTRY, PHYSICAL

ChemPhotoChem Pub Date : 2025-01-17 DOI:10.1002/cptc.202400396

Renitta Benny, Nithish Kumar, Anshuman Bera, Rakshantha Srithar, Susnata Pramanik, Sivaranjana Reddy Vennapusa, Soumen De

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Abstract

Circularly polarized excimer emission is highly sought-after due to its potential in advanced optoelectronic and sensing applications. However, achieving precise control over this phenomenon remains a significant challenge. To address this challenge, we have designed a system where circularly polarized excimer emission could be controlled via conformation locking and aggregation. The structural conformations were extensively examined using circular dichroism spectroscopy, X-ray crystallography, ¹H NMR spectroscopy, and molecular modelling. Self-assembly was triggered by adding water to THF solutions, with water-induced aggregation leading to redshifts in absorption bands and excimer emission in T1 (major monomer emission), T2 (minor monomer emission) and T3 at high water content. Additionally, the effects of aggregation on chiroptical properties were studied using circular dichroism and circularly polarized luminescence spectroscopy, revealing a reduction in circular dichroism signal and circularly polarized luminescence quenching with increasing water content. Notably, T3 displayed both excimer and monomer circularly polarized luminescence signals, reflecting two excited-state geometries. This research underscores the impact of rigidity on the photophysical and chiroptical properties of pyrene and opens avenues for further exploration of BINOL-pyrene-based macrocycles and cages.

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利用构象锁定控制比利牛斯基镊子的热学性能

圆偏振准分子发射由于其在先进光电和传感应用中的潜力而受到高度追捧。然而，实现对这种现象的精确控制仍然是一个重大挑战。为了解决这一挑战，我们设计了一个系统，其中圆极化准分子发射可以通过构象锁定和聚集来控制。利用圆二色光谱、x射线晶体学、1H核磁共振光谱和分子模型对结构构象进行了广泛的研究。在THF溶液中加水触发自组装，水诱导的聚集导致吸收带红移，高含水量时T1（主要单体发射）、T2（次要单体发射）和T3的准分子发射。此外，利用圆二色性和圆偏振发光光谱研究了聚集体对光热性质的影响，发现随着含水量的增加，圆二色性信号减弱，圆偏振发光猝灭。值得注意的是，T3同时显示准分子和单体圆偏振发光信号，反映了两种激发态几何形状。该研究强调了刚性对芘的光物理和热学性质的影响，并为进一步探索binol -pyrene基大环和笼开辟了道路。

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来源期刊

ChemPhotoChem Chemistry-Physical and Theoretical Chemistry

CiteScore

5.80

自引率

5.40%

发文量

165

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