Cuprous/Silver Iodide Hybrid Materials With Multiply Stimuli-responsive Luminescence

The organic-metal complexes with multiply Stimuli-responsive Luminescence are intelligent materials that exhibit a significant change in physical structure and chemical optical properties under minimal stimulation of the environment.As in temperature,mechanical stress,light,voltage,p H and other external stimulation showed different luminescent properties.In recent years,these complexes have potential application in many fields such as catalyst carrier,biological probe,sensor,photosensitive material and so on,and have caused widespread concerns.Due to the multiplicity of external environment stimuli,the multiply stimuli-responsive complex is more suitable,more broad application compared with the single stimuli-responsive complex.At present,for copper iodide/silver complexes are used to control the photo physical properties is mainly for chemical modification or synthesis of new ligand.However,the main control means generally require harsh reaction conditions and a longer reaction time.In comparison,the use of external stimuli regulating photo physical properties of copper iodide/silver is a simple and effective control measures.Complexes with d10 metals are well-known for their structural diversity,rich photo physical behavior,and high Luminescence efficiency.However,it is worth nothing that the majority of known chromic luminescent materials change their colors only in response to a single external stimulus.The development of doubly and multiply stimuli-responsive chromic luminescent materials is quite meaningful.In the process of studying the multiple stimuli-responsive fluorescent materials,the tetra nuclear cubic [Cu₄I₄]compounds are the subject of the this project because of their remarkable thermochromic luminescence properties and their different emission bands in various external environments.The paper focuses on the organic-metal complexes of cuprous iodide,silver iodide and its polymorphism,and explores their multiply stimuli-responsive optical properties under various external stimuli.The research work is divided into two parts:1.Tris?3-methylphenyl?phosphine?TMP?,a bulky methyl derivative ofPPh3,was selected to combine the cubane [Cu₄I₄] cores to construct a multiply stimuli-responsive chromic luminescent complex.Herein,we present a chiral C3-symmetric cubane complex [Cu₄I₄?TMP?₄]?1?with enough long Cu-Cu distances to eliminate the presence of Cu-Cu interaction and that simultaneously shows luminescent thermochromism,solvatochromism,vapochromism,and mechanochromism.This work makes us reconsider the role of Cu-Cu interaction on the chromic luminescence of copper complexes due to the apparent absence of Cu-Cu interaction in 1.Interestingly,1 can be partially converted to complexes Cu₆I₆?TMP?₄?Me CN?₂ 2 in MeCN vapor and solvent.The discovery of this phenomenon provides a deeper insight into the perception of the vapochromism and solvatochromism.2.On the basis of the study 1,the bdpp was selected to construct two groups of polymorphic cubane Cu₄I₄?bdpp?₄?3,4?and Ag4I4?bdpp?₄?5,6?under different reaction temperature.3 and 4 are a pair of cuprous iodide polymorphic complexes,which exhibit different thermochromism and mechanochromism properties due to the presence of different Cu-Cu interaction.5 and 6 are a pair of silver iodide polymorphic complexes,which exhibit different thermochromism properties due to the presence of different Ag-Ag interaction.