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Principles Of Fluorescence Spectroscopy

Dual-State Emission (DSE) in Organic Fluorophores: Design and Applications

In the present work, a novel donor (D)–acceptor (A) fluorophore based on indeno-pyrrole derivative (PYROMe) has been utilized as a dual sensor for volatile acids and aromatic amines, where sensory ...

Aggregation-Induced Emission Active Donor–Acceptor Fluorophore as a Dual Sensor for Volatile Acids and Aromatic Amines

Design and synthesis of molecular assemblies which exhibit aggregation-induced emission (AIE) have attracted persistent attention in recent years. However, studies on the impact of the substitution position in isostructural molecules to regulate aggregation-induced emission (AIE) or convert aggregation-caused quenching (ACQ) to AIE have not been reported to date. In the present study, aggregation properties of two isostructural fluorophores viz. (E)-4-(2-(anthracen-9-yl)vinyl)benzonitrile (p-AnCN) and (E)-3-(2-(anthracen-9-yl)vinyl)benzonitrile (m-AnCN), with different substitution positions have been evaluated. It was observed that m-AnCN exhibits an ACQ behavior, whereas, p-AnCN exhibits enhanced emission upon aggregation. Upon aggregation, c.a. 1.4-fold decrease in luminescence quantum yield has been observed for m-AnCN, whereas, c.a. 11-fold enhancement in luminescence quantum yield has been achieved for p-AnCN. Results from the study indicate that absence of interplay between the excited states from a dark Intramolecular Charge Transfer (ICT) state to Locally Excited state (LE) in m-AnCN is the primary reason behind the observed difference in the emission properties of the aggregates. Thus, modulation of ACQ-AIE properties has been achieved using isostructural organic fluorophores, which in turn can be used as a versatile strategy to achieve AIE-luminophores. Further, the AIE active p-AnCN aggregates have been utilized to generate three-component white light emission with CIE coordinates of (0.33, 0.33).

Achieving ACQ-AIE modulation using isostructural organic fluorophores

Three aryl-hydrazone O,N,O tridentate ligands with a different electron-withdrawing substituent were prepared. The introduction of a flexible charged chain in the ligands guaranteed solubility in many organic solvents and in water. The increasing withdrawing aptitude of the substituents red-shifted the emission in the correspondent metallopolymers. The metallated polymers were obtained by grafting ligand-zinc (II) coordination fragments onto commercial poly-(4-vinylpyridine). Metallopolymers thin films exhibited red, green and blue emission colors defined by Commission Internationale d’Eclairage (CIE) coordinates and medium to excellent photoluminescence (PL) quantum yields (PLQYs) comparable with other highly-performing active materials for Light-Emitting Diodes (LEDs). By grafting a suitable mix of the three different coordination pendants, an efficient single-component white emissive metallopolymer with CIE (0.30, 0.31) was prepared. Thanks to the charged moiety, the polymers resulted miscible with an ionic liquid. The addition produced homogeneous polymeric layers with unaltered PL performances, potentially employable in Light-emitting Electrochemical Cells (LECs).

https://www.mdpi.com/2073-4360/11/10/1712/pdf

A Highly Efficient White Luminescent Zinc (II) Based Metallopolymer by RGB Approach

Co-facial stacking can result in aggregation-caused quenching (ACQ) in conjugated organic luminogens. This study provides an attractive 'slip-stack' self-assembly approach which can eliminate the occurrence of ACQ. The obtained results from steady-state and time-resolved optical studies, along with X-ray diffraction and computational studies demonstrate aggregation-induced emission enhancement (AIEE) of a donor-π-acceptor based 1,3-diarylpropynone, namely 1-(naphthalenyl)-3-(pyren-1-yl)prop-2-yn-1-one (PYNAP). Unlike the monomer, which exhibits poor photoluminescence in solution (φf =2 % in ACN), the twisted manifold of PYNAP allows the orientation of the molecules in a slip-stack fashion during the course of aggregation, which not only avoids a direct co-facial arrangement, but also induces augmented rigidity, leading to restricted intramolecular rotation (RIR) and enhanced emission quantum yield (φf =5 % in ACN/H2 O). The aggregation behavior of PYNAP's congener, 1-phenyl-3-(pyren-1-yl)prop-2-yn-1-one (PYPH) reinforces the hypothesis that slip-stack assembly is a useful strategy for AIEE in polycyclic hydrocarbon luminogens.

Soumya Sivalingam

Papers

Effect of Slip-Stack Self-Assembly on Aggregation-Induced Emission and Solid-State Luminescence in 1,3-Diarylpropynones

Iodine-catalyzed three-component annulation: Access to highly fluorescent trisubstituted thiophenes