Novel Fluorophores--Naphthalene-Heterocycles Containing Cyano Groups: Molecular Design, Synthesis And Applications

During the investigation for this dissertation, 56 new compounds had been synthesized and identified via NMR, IR, ESI-MS and UV-Vis, etc..1. Novel 4-amino-l,8-dicyanonaphthalene (ADCN) fluorophore had been designed, and its fluorescent derivatives had been synthesized via two general procedures. The spectra studies investigated that these compounds have high fluorescence quantum yields.2. The "peri-effect promoted TICT" was suggested as a novel concept for the design of highly sensitive fluorescent probe for media polarity, based on which some 4-bissubstitutedamino-l,8-dicyanonaphthalenes had been designed; The novel "TICT promoted PET" mechanism had been suggested as novel concept for the design of highly sensitive probe for transition metal ions; Based on it and with the aid of theoretical computation, 4-(N/-methyl-)piperazino-l,8-dicyano- dicyanonaphthalene had been designed, which exhibited strongly fluorescence enhancements induced by Fe3+ and Cr3+; The ADCN derivatives with thioether substiutents had been designed and synthesized as PET fluorescent probes free of protonization, but they failed to show PET properties; Quaternary ammonium and quaternary iminonium ADCN derivatives had been designed and synthesized as water-soluble cation-type fluorescent probes, they exhibited good water-solubility.3. Under the catalysis of bases, the product of twice Knoevenagel condensation of acenaphthalenequinone and malononitrile had undergone further O2-oxidative SNArH reaction with the hydroxy ion released by the condensation, and resulted in dark-blue substitution product; Base catalyzed reactions between 5-X(-OCH3, -Br, -NO2)-acenaphthalenequinone and malononitrile led to ipso- and tele- substitutions; Under the catalysis of silica gel, and with a continuous flow method, the Knoevenagel condensation between acenaphthalenequinone and malononitrile gave the product l-biscyanomethylene-2-oxo-acenaphthalene with high yield; The 8-Oxo-8H-acenaphtho[l,2-b]pyrrol-9-carbonitrile had been obtained in quantitative yileldvia base-induced intramolecular cyclization of 1-biscyanomethylene -2-oxo-acenaphthalene under anhydrous conditions; under aqueous conditions the disproportionate of l-biscyanomethylene-2-oxo-acenaphthalene had been observed, which indicated the Knoevenagel condensation might be a reversible reaction; via the O2-oxidative SnAr" reaction of 8-Oxo-8//-acenaphtho[l,2-b]pyrrol-9-carbonitrile and hydroxy ion and primary amines, novel compounds with very strong fluorescence of long wavelength had been obtained; It was also found double-substitutions occurred on position-3 and position-6 of this precursor if the nucleophiles were six-member cyclic amines such as piperidine and morphorline.4. 4-(dimethylamino-ethylene)amino-N-allyl-l, 8-naphthalimide had been designed and synthesized as polymerizable fluorescent monomer; Its co-polymerizations with methyl methacrylate (MMA) and Styrene (ST) led to two PET fluorescent polymer probes; The Poly(MMA-co-fluorophore) exhibited considerable fluorescence enhancement toward transition metal ions, and non-sensitivity toward proton; The Poly(ST-co-fluorophore) exhibited considerable fluorescence enhancement toward proton, and fluorescence decrease toward transition metal ions.5. 3-nitro-acenaphthalenequinone and 3-nitro-l, 8-dicyanonaphthalene were designed and synthesized as novel photo-sensitive DNA cleavage agents; The tentative investigation investigated that the two compounds have good DNA cleavage ability.