Strongly blue fluorescent 1-phenyl-2-(pyridin-2-yl)-1H-phenanthro[9,10-d]imidazole(L1)is a facile block for the construction of multichromophore organic molecules,and simultaneously serves as a chelating diimine ligan...Strongly blue fluorescent 1-phenyl-2-(pyridin-2-yl)-1H-phenanthro[9,10-d]imidazole(L1)is a facile block for the construction of multichromophore organic molecules,and simultaneously serves as a chelating diimine ligand.The coordination of L1 to zinc halides enhances the intraligand charge transfer and decreases the emission energy.For the iodide derivative,intra-and intermolecular heavy atom effects lead to a dual singlet–triplet emission with a temperature-dependent ratio of fluorescence and phosphorescence bands in the crystalline state.Decoration of the anthracene core with pyridyl-phenanthroimidazole units(L2 and L3)changes the localization of the lowest energy electronic transitions to the former polyaromatic motif.The solid-state photophysical characteristics of L2 and L3-based compounds strongly depend on the intermolecular interactions between the constituting π-systems(phenanthrene and anthracene),which are perturbed by the ZnX2 coordinated fragments.Modulation of π-stacking contacts in these molecular materials containing L2 and L3 chromophores forms a basis for dynamic optical properties,responsive to mechanical,thermal,or chemical stimuli.展开更多
Multichromophoric dye-sensitized solar cells(DSSCs)based on the dual sensitization with a metal-organic combinatorial dye comprised of a ruthenium complex and an organic triphenyl amine dyad have been constructed,whic...Multichromophoric dye-sensitized solar cells(DSSCs)based on the dual sensitization with a metal-organic combinatorial dye comprised of a ruthenium complex and an organic triphenyl amine dyad have been constructed,which convert light into electrical energy with a higher power conversion efficiency and incident-photon-to-current efficiency than the devices made of individual inorganic and organic dyes.展开更多
Cyanine dyes,despite their strong near-infrared(NIR)absorption,often undergo symmetry-breaking Peierls’transitions in water known as the“cyanine limit,”resulting in suboptimal optical properties.In this work,we pre...Cyanine dyes,despite their strong near-infrared(NIR)absorption,often undergo symmetry-breaking Peierls’transitions in water known as the“cyanine limit,”resulting in suboptimal optical properties.In this work,we present a strategy to overcome this limitation by entrapping cyanine dye(Cy746)within the micellar nanoparticle(Np@M1-Cy746)of a bichromophoric[1+1]macrocycle M1 comprising of perylene diimide(PDI)and aza-BODIPY(Aza)that exhibits Forster resonance energy transfer(FRET),formed from an amphiphilic polymer 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)].This approach not only stabilizes the cyanine dye but also enables two-step FRET from PDI to Aza of the macrocycle to Cy746,resulting in panchromatic absorption,enhanced NIR emission,and achieved near-white light emission.The micellar FRET assembly Np@M1-Cy746 also serves as a ratiometric temperature sensor with a sensitivity of 0.0379%℃^(-1) and was utilized as a supramolecular photocatalyst in aqueous-phase photocatalytic Knoevenagel condensation of benzaldehyde and malononitrile.The two-step FRET process in Np@M1-Cy746 enabled its superior photocatalytic performance compared to themicelle of only M1(Np@M1),which shows one-step FRET.This study offers a distinct approach for constructing multichromophoricmacrocycle nanoparticles in aqueousmedia,leveraging upon its sequential energy transfer to achieve efficient and scalable photocatalytic transformation.展开更多
Absorption and photoluminescence spectroscopies are useful tools to study the photo-physical properties of materials. The theoretical methods for calculation of the spectra of molecules/supermolecules and aggregates, ...Absorption and photoluminescence spectroscopies are useful tools to study the photo-physical properties of materials. The theoretical methods for calculation of the spectra of molecules/supermolecules and aggregates, whose structures can differ significantly, are reviewed from the viewpoint of computational efficiency. Several model compounds/multimers are taken as examples for the spectral calculations. The numerical results achieve a satisfactory agreement between the theory and experiment.展开更多
基金the Academy of Finland(decision 317903,I.O.K.,Flagship Programme,Photonics Research and Innovation PREIN,decision 320166)the Russian Science Foundation(grant 19-73-20055,J.R.S.,photophysical studies)is gratefully acknowledged.
文摘Strongly blue fluorescent 1-phenyl-2-(pyridin-2-yl)-1H-phenanthro[9,10-d]imidazole(L1)is a facile block for the construction of multichromophore organic molecules,and simultaneously serves as a chelating diimine ligand.The coordination of L1 to zinc halides enhances the intraligand charge transfer and decreases the emission energy.For the iodide derivative,intra-and intermolecular heavy atom effects lead to a dual singlet–triplet emission with a temperature-dependent ratio of fluorescence and phosphorescence bands in the crystalline state.Decoration of the anthracene core with pyridyl-phenanthroimidazole units(L2 and L3)changes the localization of the lowest energy electronic transitions to the former polyaromatic motif.The solid-state photophysical characteristics of L2 and L3-based compounds strongly depend on the intermolecular interactions between the constituting π-systems(phenanthrene and anthracene),which are perturbed by the ZnX2 coordinated fragments.Modulation of π-stacking contacts in these molecular materials containing L2 and L3 chromophores forms a basis for dynamic optical properties,responsive to mechanical,thermal,or chemical stimuli.
基金supported by the NSF of China(21272292,61370059,21572280,61232009,91222201)NSF of Guangdong Province(S2013030013474)+1 种基金Beijing Natural Science Foundation(4152030)Special Research Fund for the Doctoral Program of Higher Education(20120171130006).
文摘Multichromophoric dye-sensitized solar cells(DSSCs)based on the dual sensitization with a metal-organic combinatorial dye comprised of a ruthenium complex and an organic triphenyl amine dyad have been constructed,which convert light into electrical energy with a higher power conversion efficiency and incident-photon-to-current efficiency than the devices made of individual inorganic and organic dyes.
基金the MoE-Scheme for Transformational and Advanced Research in Sciences(STARS)with project no.MoESTARS/STARS-2/2023-0418 for financial support of the work.
文摘Cyanine dyes,despite their strong near-infrared(NIR)absorption,often undergo symmetry-breaking Peierls’transitions in water known as the“cyanine limit,”resulting in suboptimal optical properties.In this work,we present a strategy to overcome this limitation by entrapping cyanine dye(Cy746)within the micellar nanoparticle(Np@M1-Cy746)of a bichromophoric[1+1]macrocycle M1 comprising of perylene diimide(PDI)and aza-BODIPY(Aza)that exhibits Forster resonance energy transfer(FRET),formed from an amphiphilic polymer 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)].This approach not only stabilizes the cyanine dye but also enables two-step FRET from PDI to Aza of the macrocycle to Cy746,resulting in panchromatic absorption,enhanced NIR emission,and achieved near-white light emission.The micellar FRET assembly Np@M1-Cy746 also serves as a ratiometric temperature sensor with a sensitivity of 0.0379%℃^(-1) and was utilized as a supramolecular photocatalyst in aqueous-phase photocatalytic Knoevenagel condensation of benzaldehyde and malononitrile.The two-step FRET process in Np@M1-Cy746 enabled its superior photocatalytic performance compared to themicelle of only M1(Np@M1),which shows one-step FRET.This study offers a distinct approach for constructing multichromophoricmacrocycle nanoparticles in aqueousmedia,leveraging upon its sequential energy transfer to achieve efficient and scalable photocatalytic transformation.
基金supported by the National Natural Science Foundation of China (Grant Nos. 20673104, 20833003)the 973 project (Grant Nos. 2004CB719901 and 2006CB922004)
文摘Absorption and photoluminescence spectroscopies are useful tools to study the photo-physical properties of materials. The theoretical methods for calculation of the spectra of molecules/supermolecules and aggregates, whose structures can differ significantly, are reviewed from the viewpoint of computational efficiency. Several model compounds/multimers are taken as examples for the spectral calculations. The numerical results achieve a satisfactory agreement between the theory and experiment.
