Synthesis,Structures And Properties Of Isocyanide Gold Complex

The fundamental idea of functional material design is employing external stimulation to change the molecular assembly structure,property,and especially optical characteristics,due to their crystal structure changes to the external environment?eg light,force,temperature,solvent,ions,pH,etc.?,the stimuli-responsive luminescent materials has a responsive behavior,thus can be used as an excellent optical sensor.There are many kinds of materials that can be used for irritating response luminescence,for examples:organic compounds,inorganic compounds,organometallic compounds,polymers,and liquid crystals.The structures of organometallic compounds can unite metallic bonds in inorganic compounds with covalent bonds in organic compounds,which can provide the meterials more functional possibilities.Based on the above considerations,a series of structure stable isocyanide gold compounds with excellent photophysical propertie,which induced the different halogen into aromatic hydrocarbons and then coordinated with the gold ion,are synthesized as follows:The first part:4-iodophenylisocyanochlorinated gold,2-iodophenylisocyanochl-orinated gold and 4-bromophenylisocyanochlorinated gold as precursors respectively reacted with phenylmagnesium bromide,4-fluorophenylmagnesium bromide,4-bromophenylmagnesiumbromide,3-thienylmagnesiumbromide,4-nitrilephenylmagnesium bromide,and phenylacetylene to synthesize twelve isonitrile gold complexes:[Au?C₇H₄NI??C₇H₄N?]?1?,[Au?C₇H₄NI??C₆H₄F?]?2?,[Au?C₇H₄NI??C₆H₄?]?3?,[Au?C₇H₄NI??C₈H₅?]?4?,[Au?C₇H₄NBr??C₇H₄N?]?5?,[Au?C₇H₄NBr??C₆H₄F?]?6?,[Au?C₇H₄NBr??C₆H₄?]?7?,[Au?C₇H₄NBr??C₈H₅?]?8?,[Au?C₇H₄NI??C₈H₅?]?9?,[Au?C₇H₄NI??C₆H₄Br?]?10?,[Au₃?C₇H₄NBr?₃?OCH₃?₃]?11?,[Au?C₇H₄NI??C₄H₂SBr?]?12?.The crystal structure was resolved via X-ray single crystal diffraction and then verified purity via X-ray powder diffraction.We characterized the above complexes through elemental analysis thermogravimetric analysis and infrared spectroscopy respectively.The second part:We investigated the optical properties of the above 11complexes.The fluorescence and X-ray powder diffraction analysis showed that the luminescence response of complex 1 to mechanical force and solvent was related to its phase transition.Through UV absorption spectroscopy,fluorescence spectroscopy and density functional theory?DFT?theoretical calculations,it is found that luminescence response of complex 1 to temperature is related to the lattice shrinkage of the molecule and the twist angle of the intramolecular benzene ring.Complex 5exhibits a response of luminescence to mechanical force and temperature because it is very similar to complex 1,and the remaining complexes only exhibit luminescence response to temperature,and their luminescent color at room temperature covers from the yellow light emission to the blue light emission region.This work shows that this type of materials has an adjustable wide emission range and can response to the external forces,such as mechanical force,solvents and temperature.