Synthesis And Fluorescence Characteristics Exploration Of The Lanthanide Complexes Based On Pyridine-modified Indolyl Atropisomer And Triarylborane-functionalized Do3a-Type Ligands

In the study of various organometallic complexes,lanthanide metal–organic complexes have long been paid widespread attention by virtue of features such as unique and sharp fluorescence spectrum,longer fluorescence lifetime and larger Stokes shift etc.,which are applicable to photochemistry,new optical function materials and other fields.Studies in the field of visible spectrum have shown that,by each having unique fluorescence lines in the emission spectrum,Eu(III),Tb(III)and other lanthanide metal ions can be used to produce stable,unique and efficient fluorescent molecules for lanthanide metal organic complexes as long as they are combined with appropriate organic ligands.As such,the research on organic complexes of lanthanide metal is mainly focused on the design and synthesis of novel ligands,the process of photoreaction between metal and ligand and other aspects.Herein,the synthesis of butyl-BBIB,a new pyridine-modified indolyl atropisomer,which makes pioneering use of copper-catalyzed Ullmann reactions for the formation of carbon-carbon bonds between aryl groups was introduced first.It is well known that Ullmann coupling is commonly used for coupling of C-N bonds between aryl groups.As the coupling of C-C bonds is rarely reported,the synthesis of butyl-BBIB has important practical significance to broaden the application of Ullmann coupling.Besides,as nitrogen-based atropisomer ligands are very rare among compounds of the same type,the synthesis of butyl-BBIB can help fill in gaps in the study of this field.At the same time,we also looked into the fluorescence titration reaction of the complexation of this novel ligand with Eu(III)and other lanthanide metals as well as Zn(II)and other heavy metals.Secondly,we systematically investigated the fluorescence characteristics of do3a-type ligands containing triarylboron functional groups with higher stability and the lanthanide metal complexes of such ligands,and we conducted for the first time temperature dependence fluorescence measurement of Tb(III)and Eu(III)complexes during the works for such investigations.Furthermore,another highlight of this paper is the study on variable temperature fluorescence of binary mixture system of Eu(III)and Tb(III)complexes as this binary mixture system can produce a very effective white fluorescent system and regular change of macroscopic colors has been observed when the temperature conditions change.The development of studies in the aforesaid field has important practical significance for the follow-up research on the design and synthesis of novel fluorescent probes.