The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus ...The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.展开更多
Smart materials that integrate multi-stimuli response,full reversibility,and dual-visual read-out channel are highly desired for anticounterfeiting and information encryption applications.Herein,we developed a multire...Smart materials that integrate multi-stimuli response,full reversibility,and dual-visual read-out channel are highly desired for anticounterfeiting and information encryption applications.Herein,we developed a multiresponsive perchlorate terpyridyl Pt(Ⅱ)nano complex which could undergo fully reversible conversion between three forms stimulated by water or formaldehyde molecule due to the extent of Pt–Pt interaction.Meanwhile,a dual-visual channel,i.e.,the colorimetric channel changed from yellow to orange or red and the corresponding luminescent channel from orange to orange-red or red,has also been found.The weak and equivalent strength of ion-dipole interaction and hydrogen bond that generated between formaldehyde/water and Pt(II)salt result in the easy-control reversibility between the three forms.Furthermore,by introducing different polymer matrices,1Cl·ClO_(4)@PMMA(1Cl·ClO_(4):[Pt(tpy)Cl]·ClO4,tpy:2,2':6',2''-terpyridine),PMMA:poly(methyl methacrylate))and 1Cl·ClO4@PVA(PVA:polyvinyl alcohol)are successfully constructed,which exhibit different reversible behaviors since the PMMA and PVA matrix exert different influences on the strength of hydrogen-bond.Those smart Pt(II)salt nanostructures present great potential for high-security-level anticounterfeiting application.展开更多
基金Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)Project-ID 433682494-SFB 1459 Intelligent Matter)(T.D.and T.K.)。
文摘The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.
基金support from the Major Science and Technology Project of Xinjiang(No.2022A01006-3)Science Foundation for Outstanding Young People of Xinjiang(No.2022D01E40)+1 种基金Youth Science Foundation of Xinjiang(No.2022D01C69)Tianchi Doctoral program(Nos.TCBS202130 and 51052300573).
文摘Smart materials that integrate multi-stimuli response,full reversibility,and dual-visual read-out channel are highly desired for anticounterfeiting and information encryption applications.Herein,we developed a multiresponsive perchlorate terpyridyl Pt(Ⅱ)nano complex which could undergo fully reversible conversion between three forms stimulated by water or formaldehyde molecule due to the extent of Pt–Pt interaction.Meanwhile,a dual-visual channel,i.e.,the colorimetric channel changed from yellow to orange or red and the corresponding luminescent channel from orange to orange-red or red,has also been found.The weak and equivalent strength of ion-dipole interaction and hydrogen bond that generated between formaldehyde/water and Pt(II)salt result in the easy-control reversibility between the three forms.Furthermore,by introducing different polymer matrices,1Cl·ClO_(4)@PMMA(1Cl·ClO_(4):[Pt(tpy)Cl]·ClO4,tpy:2,2':6',2''-terpyridine),PMMA:poly(methyl methacrylate))and 1Cl·ClO4@PVA(PVA:polyvinyl alcohol)are successfully constructed,which exhibit different reversible behaviors since the PMMA and PVA matrix exert different influences on the strength of hydrogen-bond.Those smart Pt(II)salt nanostructures present great potential for high-security-level anticounterfeiting application.
