具有同质多晶依赖性发射的非芳香性发光化合物

doi:10.6023/A20080368

摘要/Abstract

不含芳(杂)环、单键-重键交替单元等大共轭结构的纯有机发光材料引起了人们的广泛关注, 但其结构与发光性质间的关系仍需进一步明确. 本文研究了氧杂酸酐与氧杂酰亚胺两种非芳香性发光化合物. 通过在不同溶剂中培养单晶, 得到了具有不同发光颜色及荧光-磷光双发射的同质多晶体, 发光效率最高达17.0%. 这种高效发射可归因于含π电子与n电子基团的簇聚产生的空间共轭及构象刚硬化. 尽管这些同质多晶体结构差异微小, 但少量溶剂分子的存在导致簇聚体微环境改变, 调节了单线态与三线态发射比例, 从而产生了不同颜色的发光. 这些结果有助于人们进一步了解非典型发光化合物构象与发光间的关系, 为其机理研究与分子设计提供了新的启示.

关键词: 非芳香性发光化合物, 同质多晶, 室温磷光, 簇聚诱导发光, 空间共轭

Recently, nonconventional luminophores have received increasing attention, owing to their fundamental importance, advantages in outstanding biocompatibility, easy preparation, environmental friendliness and potential applications in sensing, imaging, encryption, etc. In order to provide more information about relationship among molecular conformation, molecular packing and emission, and moreover, to guide the design of nonconventional luminophores, molecules with definite structures and explicit molecular packing are highly desired. In this contribution, we report two nonconventional luminophores, namely F-MA and F-MI, consisting of carbonyls (C=O), electron-rich heteroatoms (O/N), and unsaturated C=C subgroups. They are nonluminous in dilute solutions while being emissive in concentrated ones. Furthermore, through crystallization in different solvents, polymorphs of both compounds with various emission colors along with distinct room temperature phosphorescence (RTP) are successfully obtained. Under 312 nm UV irradiation, three polymorphs of F-MA emit bluish-violet, blue and white lights, accompanying photoluminescence (PL) and RTP quantum efficiencies ( Φ _c/ Φ _p) of 10.6%/1.8%, 9.4%/2.1% and 2.9%/1.7%, respectively. To acquire more efficient emission, hydrogen bonds are introduced via amidation of F-MA, leading to the target compound F-MI with strikingly improved PL performance. Notably, F-MI is also polymorphic, whose Φ _c and Φ _p are of up to 17.0% and 4.8%, respectively. Meanwhile, the RTP lifetimes of F-MI polymorphs are significantly prolonged by 10- to 56-fold, as compared with their corresponding F-MA counterparts. The above PL properties can well be rationalized by the clustering-triggered emission (CTE) mechanism, namely through-space electronic delocalization of π and n electrons among different molecules in concentrated solutions or crystals alongside with sufficiently rigidified conformations is accountable for the emission, which is also verified by single crystal analysis and theoretical calculation. Besides, the noticeable RTP emission should be ascribed to the presence of C=O and heteroatoms and the clustering of such subgroups, which are ready to enhance spin-orbit coupling (SOC) and subsequent intersystem crossing transitions with effective through-space conjugation. Surprisingly, subtle changes caused by trace solvents in molecular conformations and packing modes significantly impact on intra/intermolecular interactions, which alter the relative intensity of singlet (fluorescence) and triplet (RTP) emissions, thus resulting in polymorphism-dependent emission colors. For these unorthodox luminescent molecules, their PL properties of polymorphs will deepen the understanding of the relationship between subtle structure variation and emission, thus enlightening further luminescent mechanism understanding and future rational design of novel nonconventional luminophores.

Key words: nonaromatic luminophores, polymorphism, room temperature phosphorescence, clustering-triggered emission, through-space conjugation

引用此文

来悦颖, 赵子豪, 郑书源, 袁望章. 具有同质多晶依赖性发射的非芳香性发光化合物[J]. 化学学报, 2021, 79(1): 93-99.

Yueying Lai, Zihao Zhao, Shuyuan Zheng, Wang Zhang Yuan. Polymorphism-Dependent Emission of Nonaromatic Luminophores[J]. Acta Chimica Sinica, 2021, 79(1): 93-99.

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图/表 4

图1. (a)F-MA和F-MI的化学结构、发光机理示意图及(b)其晶体主要光物理参数; 不同浓度F-MA/THF溶液在312 nm紫外灯辐照下的(c)照片与(d)发射谱; (e) 0.4 mol/L F-MA/THF溶液在不同λ ex下的发射谱; (f)不同浓度F-MA/THF溶液的吸收光谱

Figure 1. (a) Chemical structures, schematic diagram of the emission mechanism, and (b) photophysical parameters of the crystals for F-MA and F-MI. (c) Photographs and (d) emission spectra of F-MA/THF solutions at different concentrations with 312 nm UV irradiation. (e) Emission spectra of 0.4 mol/L F-MA/THF solutions at different λex. (f) Absorption spectra of F-MA/THF solutions with different concentrations

图2. F-MA同质多晶在 (a)室温及77 K时312 nm紫外线照射前后的照片, (b)即时(实线,t d=0 ms)与延迟(虚线,t d=0.1 ms)发射光谱及(c)在546, 555和542 nm的发射衰减曲线; F-MA的三种同质多晶在(d)室温及77 K下的色坐标, (e)77 K下的发射光谱(λ ex=312 nm)及(f)600, 670, 551和560 nm处的发射衰减曲线

Figure 2. (a) Photographs under and after 312 nm UV irradiation at room temperature and 77 K, (b) prompt (solid line) and delayed (dash line) emission spectra and (c) emission decay profiles monitored at 546, 555 and 542 nm at room temperature of F-MA polymorphs. (d) The chromaticity coordinate at 77 K and room temperature, (e) emission spectra (λex=312 nm) and (d) decay profiles monitored at 600, 670, 551 and 560 nm of F-MA polymorphs at 77 K

图3. F-MI同质多晶 (a)在312 nm紫外灯辐照及关闭辐照后的照片、(b)即时与延迟(t d=0.1 ms)发射光谱(λ ex=312 nm)及(c)在517, 524和529 nm处的p-RTP衰减曲线

Figure 3. (a) Photographs taken under and after ceasing the 312 nm UV irradiation, (b) prompt and delayed (td=0.1 ms) emission spectra (λex=312 nm), and (c) p-RTP decay profiles monitored at 517, 524 and 529 nm at room temperature of F-MI polymorphs

图4. (a)MA-A和(b)MI-A单晶中分子的分子内作用力和排列堆积; (c)F-MA和F-MI的单晶数据; (d)F-MA单分子和二聚体在不同能级的电子云密度分布

Figure 4. Crystal structures (298 K) with denoted intramolecular interactions and molecular packing with highlighted through-space conjugation for (a)βMA-A and (b) MI-A. (c) Single crystal data of crystals of F-MA and F-MI. (d) Electron density distributions of different orbital levels of monomer and dimer of F-MA

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