Synthesis And Properties Of Au(?)Compounds With Isocyanobenzene Bridge

In the21st century,"smart materials" have become the main material in manufacturing and life of humans, mainly because of their important practical significance and limitless application prospects. Mechanochromic materials are a class of "smart materials" with photoluminescence properties that change in response to external force stimuli. These materials are widely used in sensors, memory chips, and chemical sensor. In2001, Tang et al. reported on aggregation-induced emission (AIE) materials, an important class of anti the aggregation-caused quenching materials that more efficiently emit while in the aggregated state than in the dissolved form. Since then, AIE materials have attracted considerable research attention because of their potential applications in fields such as organic light-emitting devices and chemosensors. Most mechanofluorochromic AIE compounds were found to exhibit multistimuli-responsive fluorescence switching behaviors, and should be promising candidates for optical data storage systems, stress sensors, chemosensors, light emitting devices, and etc. AIE compounds can be expected to become a well of mechanochromic materials, and organic mechanochromic materials would no longer be rare in the future.We designed and synthesized a series of isocyano-based gold (I) complexes, and confirmed their structures, and investigated the effect of ligand structures towards unique properties. The main contents are shown as following:1. Six binuclear gold(?) complexes have been designed and synthesized in order to study the influence of the different isocyanobenzene bridge. These complexes have been characterized by IR and elemental analyses. The complexes ?-1, ?-3, ?-4and ?-6were examined by X-ray crystal diffraction. The photoluminescence spectra and X-Ray powder diffraction (XRD) studies revealed that (1) the complexe ?-1,?-2and ?-3shows reversible mechanochromic behavior, ?-4exhibits irreversible mechanochromic behavior, but ?-5and ?-6were mechanochromically inactive. Their mechanochromic properties indicated that the structure of ligand has a large effect on mechanochomic activity.2. Four novel gold(I) compound with a series different length oxygen alkyl chain substituted4-isocyanobenzene unit have been successfully designed and synthesized. These complexes have been characterized by1H NMR,19F NMR, IR and elemental analyses. The complexes ?-1,?-3and ?-4were examined by X-ray crystal diffraction. The photoluminescence spectra and X-Ray powder diffraction (XRD) studies revealed that it is AIE-active. And it is aggregation-induced emission (AIE) active by means of the absorption spectral and photoluminescence studies. It is AIE-active and thermochromic since:(1) the addition of water to solutions of1in common organic solvents (EtOH) formed two kinds of nano-aggregates, showing blue and yellow-green emission;(2) the emission of1can be switched between "blue" and "yellow-green" repeatedly using simple heating-cooling cycles.3. To explore metal compounds with novel structures and unique properties, seven new isocyanobenzene binuclear gold(?) complexes linked by a series different length flexible chain have been designed and synthesized. These complexes have been characterized by1H NMR,19F NMR, IR and elemental analyses. The photoluminescence spectra and X-Ray powder diffraction (XRD) studies revealed that seven binuclear gold(?) complexes shows switchable mechanochromic luminescence, which can be switched between "off" and "on" repeatedly using simple grinding-heating cycles. The complexe IV-l-IV-4exhibited better aggregation-induced emission (AIE) active for the complexe IV-5-IV-6by means of the absorption spectral and photoluminescence studies.4. Three isocyanobenzene binuclear gold(?) complexes, in which the centre bridge was structural isomerism, have been designed and synthesized. These complexes have been characterized by1H NMR,19F NMR, IR and elemental analyses. The photoluminescence spectra and X-Ray powder diffraction (XRD) studies revealed that (1) the complexe ?-1shows reversible mechanochromic luminescence, which can be switched between "blue" and "green" repeatedly using simple grinding-heating cycles;(2) the complexe ?-2shows switchable mechanochromic luminescence;(3) the complexe ?-3shows green luminescence, and no mechanochromic property. The absorption spectral and photoluminescence studies exhibited that three gold(?) complexes was aggregation-induced emission (AIE) active.5. A novel gold(?) complexes with a dithienylethene bridge have been synthesized. Complexe ?-1was examined by IR and elemental analyses. Complexe ?-2was characterized by1H NMR,19F NMR, IR and elemental analyses. Absorption spectral changes have revealed that metallic has substantially promoted the performance of photochromic compounds. But it is regrettable that complexe ?-1and ?-2have no mechanochromic property and AIE.