Synthesis And Characterization Of Grinding-responsive Luminescent Copper(?) Pyridyltetrazolyl Complexes

Stimuli-responsive smart materials have been widely studied due to their potential applications in sensing and detection,anti-counterfeiting materials,and information recording and storage.Due to rich abundance,low cost,and environmental benignancy of Cu and unique luminescence of copper(?)complexes,it is very important to develop stimuli-responsive luminescent materials by using copper(?)complexes.In this thesis,two classes of stimuli-responsive copper(?)luminescent complexes were designed and synthesized by using functional pyridyltetrazole ligands,and the stimuli-responsive mechanism,structures,and photophysical properties have been systematacially and thoroughly studied.The detailed research contents are as follows:1.A series of mechanochromic luminescent tetranuclear copper(?)complexes 1-5 were designed and synthesized by using functional 5-(2'-pyridyl)tetrazole ligands and N,N-bis(diphenylphosphino)amine(dppa).Complexes 1-5 are all doubly charged tetranuclear Cu(I)complexes containing two Cu₂P4N2 eight-membered of {Cu₂(?-dppa)2} units showing the boat-chair configuration.The two {Cu₂(?-dppa)2} moieties are connected by two N-H deprotonated functionalized 5-(2'-pyridyl)tetrazole ligands in a mono-anionic?3-?2(N1,N2),?1(N3),?1(N4)tetradentate coordination mode,resulting in four seven-membered Cu₂P2N3 rings and one almost coplanar Cu₂N4 six-membered ring.These constitute a new larger coplanar {Cu4[?3-?2(N,N),?1(N),?1(N)-diimine]2}2+unit.The research results show that all of these Cu(I)complexes exhibit eversible mechanochromic luminescence,which may be due to the disruption and restoration of intramolecular ?…?interactions between the pyridyl and phenyl rings caused by mechanical grinding and exposure to CH2Cl2 vapor.This has also been confirmed by their X-ray powder diffraction(PXRD)and Fourier transform infrared(FT-IR)studies at various states.2.On the basis of previous work,we used bis(diphenylphosphine)methane(dppm)instead of N,N-bis(diphenylphosphino)amine(dppa)and 5-(3'-methyl-2'-pyridyl)tetrazole tetrazole(mpytzH)to design and synthesize a blue-emitting 6-b with similar structure to 1-5.By optimizing the crystallization solvent,we obtained another yellow-emitting crystal complex 6-y.The blue-emitting complex 6-b exhibits mechanochromic luminescence similar to complexes 1-5,while the yellow emitting complex 6-y does not exhibit mechanochromic luminescence.Interestingly,when the yellow emitting complex 6-y is exposed to acetone vapor for a period of time,it emits blue emission under UV irradiation and shows the same mechanochromic luminescence as complex 6-b.The results show that the structures and properties of these two complexes are mainly due to the destruct and recovery of intramolecular "pyridyl/phenyl" ?…? interactions,which has been confirmed by X-ray single crystal structural analysis and theoretical calculation of 6-b and 6-y and their X-ray powder diffractions and Fourier transform infrared spectrometry in various states.