Multi‐C−C/C−N‐Coupled Light‐Emitting Aliphatic Terpolymers: N−H‐Functionalized Fluorophore Monomers and High‐Performance Applications

Abstract

To circumvent costly fluorescent labeling, five nonconventional, multifunctional, intrinsically fluorescent aliphatic terpolymers (1–5) have been synthesized by C−C/C−N‐coupled, solution polymerization of two non‐emissive monomers with protrusions of fluorophore monomers generated in situ. These scalable terpolymers were suitable for sensing and high‐performance exclusion of CuII, logic function, and bioimaging. The structures of the terpolymers, in situ attachment of fluorescent monomers, aggregation‐induced enhanced emission, bioimaging ability, and super adsorption were investigated by 1H and 13C NMR, EPR, FTIR, X‐ray photoelectron, UV/Vis, and atomic absorption spectroscopy, thermogravimetric analysis, high‐resolution transmission electron microscopy, dynamic light scattering, solid‐state fluorescence, fluorescence imaging, and fluorescence lifetime measurements, as well as by isotherm, kinetics, and thermodynamic studies. The geometries and electronic structures of the fluorophores and the absorption and emission properties of the terpolymers were examined by DFT, time‐dependent DFT, and natural transition orbital analyses. For 1, 2, and 5, the limits of detection were determined to be 1.03×10−7, 1.65×10−7, and 1.77×10−7 m, respectively, and the maximum adsorption capacities are 1575.21, 1433.70, and 1472.21 mg g−1, respectively.

Nonconjugated Biocompatible Macromolecular Luminogens for Sensing and Removals of Fe(III) and Cu(II): DFT Studies on Selective Coordination(s) and On‐Off Sensing

“…[ 22 ] Indeed, a monomer bearing tertiary amide side chain should endow more rigidity and fluorescence of polymeric luminogens compared to monomers comprising primary or secondary amide functionality. [ 23 ]…”

“…Notably, the surfactant‐free facile solution polymerization is better than that of surfactant‐assisted conventional emulsion polymerization for attaining the clusterization and AEE by the inter‐/intra‐molecular hydrogen bonding and hydrophobic interactions of polymers. [ 23 ] Here, N ‐(methylol)acrylamide (NMA) has been chosen as common comonomer for synthesizing P1 and P2 , as its side chain is expected to function as an in situ comonomer attachment site by the N–H activation. Moreover, NMA, a secondary amide with OH as hydrogen bonding site, can confer better rigidity in terpolymers.…”

“…[22] Indeed, a monomer bearing tertiary amide side chain should endow more rigidity and fluorescence of polymeric luminogens compared to monomers comprising primary or secondary amide functionality. [23] Thus, an increasing in situ conversion of secondary to tertiary amides should be advantageous for elevating rigidity, N-branching, and fluorescence of aliphatic macromolecules. In polymers, carbonyl functionalities and N-branched tertiary amide favor the intrinsic fluorescence by forming the donoracceptor complexes.…”

Fluorescent Terpolymers Using Two Non-Emissive Monomers for Cr(III) Sensors, Removal, and Bio-Imaging

“…NTO Analysis. For determining individual electron property, 20 hole−electron wave function overlap (σ he ) and separation (Δr) between hole and electron distribution in S 1 , S 2 , and S 3 are envisaged in Table S14, wherein the results revealed local emissions (LEs)/CT transitions of 1, 2, and 3. The NTO results identified the exact locations of holes and electrons in terpolymers.…”

Synthesis of Nonaromatic Macromolecular Luminogens, DFT Studies on Photophysics, and O‐Donor Selective On−Off Sensors: Contributions of In Situ N‐(Methylol)Acrylamido Comonomers

“…Moreover, the larger wavelengths of emission maxima in DMSO compared to that in more polar CH 3 OH confirmed that hydrogen bonding interactions in polar protic solvents and polarity changed the peaks of ML1/ML2, and presented important roles in nonconventional intrinsic fluorescence of ML1/ML2. [54] The emissions (excitation-dependent) of ML1 and ML2 were confirmed by the shifting of spectra to higher λ em at larger wavelength of excitations (λ ex ) (Figure S6, Supporting Information). [55] In this regard, shifting toward higher λ em confirmed the presence of blue-emissive aggregates and emissive traps in each aggregate of ML1/ML2.…”