High-contrast mechanochromic(MC)materials are prominent candidates for sensor,security,and memory applications;however,the development of materials with a large luminescence change(Δλem>100 nm)under external stim...High-contrast mechanochromic(MC)materials are prominent candidates for sensor,security,and memory applications;however,the development of materials with a large luminescence change(Δλem>100 nm)under external stimuli is challenging.Considering that polymorphic molecules usually exhibit reversible mechanochromism,polymorph prediction is adopted for thefirst time to guide the design of high-contrastMC materials in this study.We designed and synthesized a series of donor–π–acceptor pyran derivatives bearing different electron donors and acceptors as model systems.The polymorph prediction indicated that 4-dicyanomethylene-2,6-distyryl-4H-pyran and 4H-pyran-4-one derivatives had the potential to crystallize in both monomer andπ-dimer aggregates,while barbituric acid-based compound tended to pack tightly in all aggregated states.The experimental results agreed well with the prediction that the derivatives potentially possessing both monomer andπ-dimer aggregate structures exhibit excellent MC behavior,whereas the fluorescence difference for the barbituric acid-based compounds is minimal.Moreover,a compound with an excellent fluorescence difference of three colors during reversible mechanochromism was chosen as the candidate for an optical recording material and security ink.This work proposes an effective method to guide the design of stimuli-responsive materials,which may open promising avenues for the development of high-contrast MC molecules.展开更多
基金This research was made possible as a result of a generous grant from National Natural Science Foundation of China(nos.21472111 and 21877013)the 111 Project(no.D20015).
文摘High-contrast mechanochromic(MC)materials are prominent candidates for sensor,security,and memory applications;however,the development of materials with a large luminescence change(Δλem>100 nm)under external stimuli is challenging.Considering that polymorphic molecules usually exhibit reversible mechanochromism,polymorph prediction is adopted for thefirst time to guide the design of high-contrastMC materials in this study.We designed and synthesized a series of donor–π–acceptor pyran derivatives bearing different electron donors and acceptors as model systems.The polymorph prediction indicated that 4-dicyanomethylene-2,6-distyryl-4H-pyran and 4H-pyran-4-one derivatives had the potential to crystallize in both monomer andπ-dimer aggregates,while barbituric acid-based compound tended to pack tightly in all aggregated states.The experimental results agreed well with the prediction that the derivatives potentially possessing both monomer andπ-dimer aggregate structures exhibit excellent MC behavior,whereas the fluorescence difference for the barbituric acid-based compounds is minimal.Moreover,a compound with an excellent fluorescence difference of three colors during reversible mechanochromism was chosen as the candidate for an optical recording material and security ink.This work proposes an effective method to guide the design of stimuli-responsive materials,which may open promising avenues for the development of high-contrast MC molecules.
