Design and Development of Distinct Tetracyanoquinodimethane Derivatives Exhibiting Dual Effect of Fluorescence and Anticancer Activity

Abstract

Tetracyanoquinodimethane (TCNQ) is known to react with primary/secondary amines to generate mono/di‐substituted TCNQ derivatives resulting in optical (fluorescence) and non‐linear optical characteristics. However, the choice of amine plays a key role in the sequel of certain material attributes. Nevertheless, demonstration of TCNQ derivatives, specifically obtained by reacting TCNQ with simple & small amine side chains of existing anticancer drugs, emerging in dual effect of fluorescence as well as anticancer activity, is not explored so far and has been still existing as a gap in TCNQ related research. Additionally, mono/di‐substituted TCNQ's owning strong fluorescence in solutions (∼10 to 104 order) than their solids are still lacking and are in need to be generated. In this regard, we aimed to synthesize straightforward TCNQ derivatives in single step by reacting TCNQ with specific (simple and small) amines being side chains of existing anticancer drugs (a contemporary design approach) and successfully obtained novel mono/di‐substituted TCNQ derivatives manifesting dual effect of fluorescence and anticancer activity. In this fashion, we have avoided the usage of bulky main moiety of an anticancer molecule, since our aim was not to use the total anticancer drug as such, like in a Pro‐drug preparation, but we intended to use the minimal part of an anticancer drug to invent novel TCNQ derivatives as anticancer active fluorophores. Wavelength of maximum emission for all the five potent molecules was within ∼525 nm‐696 nm. All compounds showed moderate anticancer activity against different cancer cell lines and IC50 values were in the range of 11 to 49 μM, when the synthesized novel compounds were tested in B16F10, MDA‐MB‐231 and A549 cell lines. Henceforth, this study has emanated in the first generation TCNQ derivatives as organic fluorescent anticancer active molecules.

Efficient Standalone Flexible Small Molecule Organic Solar Cell Devices: Structure-Performance Relation Among Tetracyanoquinodimethane Derivatives

“…Though noncovalent intermolecular interactions (∼2.70 to 3.23 Å) were dominant in 4 , stronger H-bonding was seen among N2···H6 (1.950 Å); further, 4 exhibited supramolecular assemblies as well (Figure S12b). The PXRD pattern showed sharp and intense peaks for all 1 – 4 , confirming crystalline attributes (Figure S13).…”

“…Also, 4 showed π−π stacking and extensive short contacts in the crystal lattice. 21 The PCE of 3 was found to be 2.58%, less than that of 4, though 3 also has an aromatic substituent, possibly due to minimal crystallinity (Figure 4c), and the presence of −CF 3 and −CN adding an -I effect decreases the π-electron density over the aromatic ring to be available for stacking. Further, the absence of an aromatic ring substituent and the presence of solely aliphatic amine depicts the lowest PCE for 2 (PCE = 2.12%) among 1−4.…”

“…However, in recent times, 2 exhibited an appreciable fluorescence property with a quantum yield (Φ f ) = ∼0.4% in solution and a Φ f of ∼50% in a solid. Further, 3 and 4 each possess strong electron-withdrawing groups, an induced redshift, and a large Stokes shift of ∼126 and 152 nm, respectively . Nevertheless, the photophysical property of 1 is yet unrevealed.…”

Unprecedented transformation from cyclized zwitterionic oxazolidine derivatives to corresponding non-zwitterionic aromatic amides via Vilsmeier reagent in a one-pot reaction: optical property and crystallography

“…conformational change governed by crystal lattices result in enhanced fluorescence. 30,57 Moreover, when 0 to 90% Millipore (18 MO) water fraction (f w ) was added to 10 ppm solutions of [1] and [2] in DMSO, the emission intensity decreased from 20% f w in [1] and [2] indicative of aggregation quenching. A linear response in the decreased emission intensity was observed in [3]; [4] also manifested the same from 10% f w (Fig.…”

“…Recently, investigation of photoluminescence of DADQs has been conducted. TCNQ on reaction with various heterocyclic, [19][20][21][22][23][24] aliphatic, [5][6][7][8][9][10][11][12][13][14] and countable (B5) aromatic amines 8,9,[25][26][27] has led to interesting features such as aggregation-induced solid-state (solids/thin films) emission, 10,22,[28][29][30] colloids, 9 nanoparticles, [31][32][33] phase change behavior, 6,11,34 and second harmonic generation. 12,[35][36][37] Of late, diaminodicyanoquinones with benzene moiety in the amine substituents accompanied by non-covalent interactions, H-bonding and molecular self-assembly manifested B90% quantum yield.…”