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

Abstract The development of intrinsically luminescent multifunctional macromolecules and understanding their fluorescence characteristics are highly desirable to broaden further the scope of nontraditional macromolecular luminogens. Here, two nontraditional macromolecular luminogens, such as 2‐(methacryloyloxy)ethanol‐co‐2‐hydroxyethyl 3‐(N‐(methylol)acrylamido)‐2‐methylpropanoate‐co‐N‐(methylol)‐2‐propenamide (MAE‐co‐HENMAMMP‐co‐NMPA, ML1) and 2‐methylenesuccinic acid‐co‐2‐((N‐(methylol)acrylamido)methyl)succinic acid‐co‐N‐(methylol)‐2‐propenamide (MSA‐co‐NMAMMSA‐co‐NMPA, ML2) are synthesized via in situ inclusions of N‐(methylol)acrylamido‐ester and N‐(methylol)acrylamido‐acid comonomers by the polymerization of two synthetic monomers. These luminogens are suitable for sensing alongside exclusion of paramagnetic ions, i.e., Cu(II) and Fe(III). The structures of ML1 and ML2, in situ protruded HENMAMMP/NMAMMSA, and aggregation‐enhanced emissions (AEEs) are explored thoroughly. The through‐space electronic interactions from n/π of HENMAMMP + NMPA and NMAMMSA + MSA fragments to π* of HENMAMMP + MAE and NMAMMSA in ML1 and ML2, respectively, and hydrogen bonding among >CON− of HENMAMMP and −CONH− of NMPA in ML1 and −COOH/−COOH of MSA and −COOH/−CH₂OH of NMAMMSA in ML2 collectively form clusteroluminogens, comprehended by reduced density gradient (RDG) calculations. The O‐donor selective coordinative interactions of paramagnetic Cu(II) and Fe(III) and substantial adsorption from aqueous solutions (concentrated) are analyzed through X‐ray photoelectron spectroscopy (XPS) spectra and density functional theory (DFT) studies of ML1/ML2 and Cu(II)‐ML1/Fe(III)‐ML2.