The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)]...The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)](1) is reported, which contains two organic amines cations and one [MnBr_(4)] tetrahedral ion. Compound 1 has a dielectric anomaly signal at 338 K, which proves its thermodynamic phase transition. The single crystal measurements at 200 K and 380 K show that the phase transition of compound 1 is caused by the thermal vibration of organic amine cations in the lattice. Moreover, compound 1 shows yellow-green luminescence under UV light irradiation. The magnetism measurements indicate that compound 1 shows switchable magnetic properties. This organic–inorganic material is a multifunctional material with dielectric, optical, and magnetic synergetic switchable effects, which expands a new direction for designing multifunctional materials.展开更多
Significant developments have been made in the past few decades for lanthanide(Ln)ions doped fluorosilicate glass-ceramics(Flusi-GCs).As novel generation of luminescence materials with a wide range of applications,Flu...Significant developments have been made in the past few decades for lanthanide(Ln)ions doped fluorosilicate glass-ceramics(Flusi-GCs).As novel generation of luminescence materials with a wide range of applications,Flusi-GCs as a single host combine the advantages of glass and ceramics/crystals as well as fluorides and silicates.In this review,the chemical design principles and experimental procedures of Flusi-GCs are summarized in detail.Flusi-GCs are categorized as those containing PbxCd_(1-x)F_(2),RF_(3)(R=Y,La,Gd),MF_(2)(M=Ca,Sr,Ba),xMF_(2)-yRF_(3)(R=Y,La-Lu),mAF-nRF_(3)(A=Li,Na,K),KTF_(3)(T=Zn,Mn)and K2 SiF6 nanocrystals(NCs).Theoretical breakthroughs mainly by molecular dynamic(MD)simulation have been recapitulated as efficient routes for composition-design,nano-crystallization-prediction,and performance-optimization of Flusi-GCs containing target fluoride NCs.Essential research progresses pertaining photonic applications have been made in random lasers,communication amplifiers,optical fibers,spectral converters,white light-emitting-diodes(WLEDs),and thermal sensors.In the end,we propose three future research directions for Flusi-GCs.展开更多
In nanoscience, molecular switches have played a significant role to deliver different control abilities to practical functions,whereas high-contrast luminescence switchable manipulation at nanoscale is still limited....In nanoscience, molecular switches have played a significant role to deliver different control abilities to practical functions,whereas high-contrast luminescence switchable manipulation at nanoscale is still limited. Since the tuning for emission behavior with high contrast ratio strongly connects to numerous visualized sensing and optoelectronic applications, we here report that autonomous p H control can be enrolled to address a high-contrast molecular emission change at the nanoaggregated level, for gaining a flicker luminescence performance in aqueous media. Employing a BODIPY contained dynamic covalent dye, we find its luminescent signal and nanoaggregate size can be spontaneously adjusted in water. On this basis, high-contrast luminescence switching of the material can be achieved upon the alternate introduction of base and acid into the aggregation state. Such a behavior can be attributed to a p H triggered photo-induced electron transfer regulation process. The dye aggregates can be well endocytosed for bioimaging and its luminescent variation can be autonomously displayed as a flicker effect. These results provide new visions for the design and development of smart materials with a dynamic luminescence behavior.展开更多
The emergence of endoscopy for the diagnosis of gastrointestinal diseases and the treatment of gastrointestinal diseases has brought great changes.The mere observation of anatomy with the imaging mode using modern end...The emergence of endoscopy for the diagnosis of gastrointestinal diseases and the treatment of gastrointestinal diseases has brought great changes.The mere observation of anatomy with the imaging mode using modern endoscopy has played a significant role in this regard.However,increasing numbers of endoscopies have exposed additional deficiencies and defects such as anatomically similar diseases.Endoscopy can be used to examine lesions that are difficult to identify and diagnose.Early disease detection requires that substantive changes in biological function should be observed,but in the absence of marked morphological changes,endoscopic detection and diagnosis are difficult.Disease detection requires not only anatomic but also functional imaging to achieve a comprehensive interpretation and understanding.Therefore,we must ask if endoscopic examination can be integrated with both anatomic imaging and functional imaging.In recent years,as molecular biology and medical imaging technology have further developed,more functional imaging methods have emerged.This paper is a review of the literature related to endoscopic optical imaging methods in the hopes of initiating integration of functional imaging and anatomical imaging to yield a new and more effective type of endoscopy.展开更多
Cutting-edge technologies in optical molecular imaging have ushered in new frontiers in cancer research, clinical translation, and medical practice, as evidenced by recent advances in optical multimodality imaging, Ce...Cutting-edge technologies in optical molecular imaging have ushered in new frontiers in cancer research, clinical translation, and medical practice, as evidenced by recent advances in optical multimodality imaging, Cerenkov luminescence imaging(CLI), and optical imageguided surgeries. New abilities allow in vivo cancer imaging with sensitivity and accuracy that are unprecedented in conventional imaging approaches. The visualization of cellular and molecular behaviors and events within tumors in living subjects is improving our deeper understanding of tumors at a systems level. These advances are being rapidly used to acquire tumor-to-tumor molecular heterogeneity, both dynamically and quantitatively, as well as to achieve more effective therapeutic interventions with the assistance of real-time imaging. In the era of molecular imaging, optical technologies hold great promise to facilitate the development of highly sensitive cancer diagnoses as well as personalized patient treatment—one of the ultimate goals of precision medicine.展开更多
The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline （DICNQ） by solvothermal reaction gives rise to a coordination polymer [CdCl2（DICNQ）]n 1. Single-crystal X-ray diffraction analysis reveals that the compoun...The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline （DICNQ） by solvothermal reaction gives rise to a coordination polymer [CdCl2（DICNQ）]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1： a = 6.756（1）, b = 35.371（6）, c = 7.027（1）A , V = 1679.1（5） A^3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm^3, μ = 1.630 mm-1, F（000） = 904, S = 1.005 and T = 293（2） K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I 〉 2σ（I）, and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states （DOS） calculations.展开更多
The modification of o-acetylsalicylic acid by 3-aminopropyl triethoxysilane (APS) was achieved and the assembly of their corresponding organic-inorganic molecular-based hybrid material with the two moieties bridged by...The modification of o-acetylsalicylic acid by 3-aminopropyl triethoxysilane (APS) was achieved and the assembly of their corresponding organic-inorganic molecular-based hybrid material with the two moieties bridged by covalent bonds was obtained. It is utilized to coordinate to terbium ions and further happened hydrolysis and polycondensation processes by chemical active triethoxysilyl groups. The photophysical properties show that the triplet energy of modified o-acetylsalicylic acid is efficiently responsible for the antenna effect and matches with the emissive energy level of metal ions. Consequently, the intramolecular energy transfer process completed within these molecular-based hybrids and strong green emission of Tb 3+ was achieved.展开更多
The silver-dppm complex, [Ag2（dppm）2（NMP）2]（SbF6）2-4H2O-3CH2Cl2 1 （NMP = 2- （4-dimethylaminophenyl）imidazo（4,5-f）（1,10）phenanthroline, dppm = diphenylphosphinomethane）, was synthesized and its structure ...The silver-dppm complex, [Ag2（dppm）2（NMP）2]（SbF6）2-4H2O-3CH2Cl2 1 （NMP = 2- （4-dimethylaminophenyl）imidazo（4,5-f）（1,10）phenanthroline, dppm = diphenylphosphinomethane）, was synthesized and its structure was determined by X-ray diffraction. The crystal belongs to monoclinic, space group C2/c, Mr = 2461.61, a = 21.57（10）, b = 22.48（6）, c = 22.53（6）A, β= 101.29（2）°, V= 10713（64）A^3, Z= 4, Dc= 1.526 g/cm^3,μ= 1.141mm^-1, F（000） = 4920, R =0.0664 and wR = 0.1774 for 8524 observed reflections （1 〉 2σ（I））. Complex 1 exists as a centrosymmetric dimmer. The two dppm molecules bridge two AgNMP moieties to form an eight-membered Ag2P4C2 metallacyclic ring with ligand NMP chelating to each Ag. It appears photoluminescence （λmax = 625 nm） at room temperature and makes red shift compared with free ligand NMP （λmax = 522 nm）. DFF calculation indicates that the emission of 1 originates from singlet metal-perturbed ILCT excited state.展开更多
Three-primary-color luminescent materials are highly desirable to construct white-light emitting resource,multi-color optical displays,and tunable photonic applications.However,the efficient strategy to establish the ...Three-primary-color luminescent materials are highly desirable to construct white-light emitting resource,multi-color optical displays,and tunable photonic applications.However,the efficient strategy to establish the three-primary-color systems with unique photofunctionalities is still rather limited,particularly for molecular materials.Herein,we developed a molecular cocrystal route to obtain three-primary-color emissive materials by tuning different donor-acceptor units based on the same chromophore(4,4′-bis(2,5-dimethylstyryl)biphenyl,Bdb).The warm and cold white-light together with multi-color emission in most of visible region can be highly adjusted by rationally tuning different mixture components of three-primary-color cocrystals through an energy transfer mechanism.Furthermore,the blue/green/red emitters endow Bdb molecular cocrystals novel colortunable photonic properties(such as one-dimensional(1D)/2D optical waveguide,polarized fluorescence,up-conversion luminescence,and amplified spontaneous emission),benefitting from their well-defined micro/nanostructures and high crystallinity.Particularly,the high luminescence quantum yield(82.49%)and polarized anisotropy(0.723)outperform most of state-ofthe-art molecular crystalline materials.Therefore,this work supplies an effective way to fabricate new types of three-primarycolor phosphors through luminescent cocrystals,which have promising applications in the fields of full-color displays,whitelight irradiation,low-dimensional optical polarization,and micro/nanophotonics.展开更多
The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comp...The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comparing theoretical and expe rimental electronic circular dichroism spectra.The e nantiopure cryptates exhibit strong circularly polarized luminescence with a maximum dissymmetry factor glum=0.25 for the f-f transition 5 D0→7 F1(λ=594 nm)under visible light excitation atλgx=400 nm.展开更多
基金supported by the the National Natural Science Foundation of China (Nos.21875093, 22161002 and22105089)Natural Science Foundation of Jiangxi Province (Nos.20224BAB214005, 20204BCJ22015 and 20202ACBL203001)Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry (No.20212BCD42018)。
文摘The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)](1) is reported, which contains two organic amines cations and one [MnBr_(4)] tetrahedral ion. Compound 1 has a dielectric anomaly signal at 338 K, which proves its thermodynamic phase transition. The single crystal measurements at 200 K and 380 K show that the phase transition of compound 1 is caused by the thermal vibration of organic amine cations in the lattice. Moreover, compound 1 shows yellow-green luminescence under UV light irradiation. The magnetism measurements indicate that compound 1 shows switchable magnetic properties. This organic–inorganic material is a multifunctional material with dielectric, optical, and magnetic synergetic switchable effects, which expands a new direction for designing multifunctional materials.
基金This work was supported by the National Key R&D Program of China(No.2016YFA0200601)the National Natural Science Foundation of China(No.21790352)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB36000000)the Anhui Initiative in Quantum Information Technologies(No.AHY090100).
基金Project supported by National Natural Science Foundation of China(51872255,51672243)。
文摘Significant developments have been made in the past few decades for lanthanide(Ln)ions doped fluorosilicate glass-ceramics(Flusi-GCs).As novel generation of luminescence materials with a wide range of applications,Flusi-GCs as a single host combine the advantages of glass and ceramics/crystals as well as fluorides and silicates.In this review,the chemical design principles and experimental procedures of Flusi-GCs are summarized in detail.Flusi-GCs are categorized as those containing PbxCd_(1-x)F_(2),RF_(3)(R=Y,La,Gd),MF_(2)(M=Ca,Sr,Ba),xMF_(2)-yRF_(3)(R=Y,La-Lu),mAF-nRF_(3)(A=Li,Na,K),KTF_(3)(T=Zn,Mn)and K2 SiF6 nanocrystals(NCs).Theoretical breakthroughs mainly by molecular dynamic(MD)simulation have been recapitulated as efficient routes for composition-design,nano-crystallization-prediction,and performance-optimization of Flusi-GCs containing target fluoride NCs.Essential research progresses pertaining photonic applications have been made in random lasers,communication amplifiers,optical fibers,spectral converters,white light-emitting-diodes(WLEDs),and thermal sensors.In the end,we propose three future research directions for Flusi-GCs.
基金supported by the National Natural Science Foundation of China (21628401)the National Program for Thousand Young Talents of China
文摘In nanoscience, molecular switches have played a significant role to deliver different control abilities to practical functions,whereas high-contrast luminescence switchable manipulation at nanoscale is still limited. Since the tuning for emission behavior with high contrast ratio strongly connects to numerous visualized sensing and optoelectronic applications, we here report that autonomous p H control can be enrolled to address a high-contrast molecular emission change at the nanoaggregated level, for gaining a flicker luminescence performance in aqueous media. Employing a BODIPY contained dynamic covalent dye, we find its luminescent signal and nanoaggregate size can be spontaneously adjusted in water. On this basis, high-contrast luminescence switching of the material can be achieved upon the alternate introduction of base and acid into the aggregation state. Such a behavior can be attributed to a p H triggered photo-induced electron transfer regulation process. The dye aggregates can be well endocytosed for bioimaging and its luminescent variation can be autonomously displayed as a flicker effect. These results provide new visions for the design and development of smart materials with a dynamic luminescence behavior.
文摘The emergence of endoscopy for the diagnosis of gastrointestinal diseases and the treatment of gastrointestinal diseases has brought great changes.The mere observation of anatomy with the imaging mode using modern endoscopy has played a significant role in this regard.However,increasing numbers of endoscopies have exposed additional deficiencies and defects such as anatomically similar diseases.Endoscopy can be used to examine lesions that are difficult to identify and diagnose.Early disease detection requires that substantive changes in biological function should be observed,but in the absence of marked morphological changes,endoscopic detection and diagnosis are difficult.Disease detection requires not only anatomic but also functional imaging to achieve a comprehensive interpretation and understanding.Therefore,we must ask if endoscopic examination can be integrated with both anatomic imaging and functional imaging.In recent years,as molecular biology and medical imaging technology have further developed,more functional imaging methods have emerged.This paper is a review of the literature related to endoscopic optical imaging methods in the hopes of initiating integration of functional imaging and anatomical imaging to yield a new and more effective type of endoscopy.
文摘Cutting-edge technologies in optical molecular imaging have ushered in new frontiers in cancer research, clinical translation, and medical practice, as evidenced by recent advances in optical multimodality imaging, Cerenkov luminescence imaging(CLI), and optical imageguided surgeries. New abilities allow in vivo cancer imaging with sensitivity and accuracy that are unprecedented in conventional imaging approaches. The visualization of cellular and molecular behaviors and events within tumors in living subjects is improving our deeper understanding of tumors at a systems level. These advances are being rapidly used to acquire tumor-to-tumor molecular heterogeneity, both dynamically and quantitatively, as well as to achieve more effective therapeutic interventions with the assistance of real-time imaging. In the era of molecular imaging, optical technologies hold great promise to facilitate the development of highly sensitive cancer diagnoses as well as personalized patient treatment—one of the ultimate goals of precision medicine.
基金Supported by the NNSFC (20701037, 90922035)973 program (2009CB939801)+1 种基金Key Project from the CAS (KJCX2.YW.M10)the NSF of Fujian Province (2008I0026, 2008F3115)
文摘The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline （DICNQ） by solvothermal reaction gives rise to a coordination polymer [CdCl2（DICNQ）]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1： a = 6.756（1）, b = 35.371（6）, c = 7.027（1）A , V = 1679.1（5） A^3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm^3, μ = 1.630 mm-1, F（000） = 904, S = 1.005 and T = 293（2） K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I 〉 2σ（I）, and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states （DOS） calculations.
文摘The modification of o-acetylsalicylic acid by 3-aminopropyl triethoxysilane (APS) was achieved and the assembly of their corresponding organic-inorganic molecular-based hybrid material with the two moieties bridged by covalent bonds was obtained. It is utilized to coordinate to terbium ions and further happened hydrolysis and polycondensation processes by chemical active triethoxysilyl groups. The photophysical properties show that the triplet energy of modified o-acetylsalicylic acid is efficiently responsible for the antenna effect and matches with the emissive energy level of metal ions. Consequently, the intramolecular energy transfer process completed within these molecular-based hybrids and strong green emission of Tb 3+ was achieved.
基金This work was support by National Basic Research Program of China (No: 2004CB720605) and the Natural Science Foundation of China (No. 20173064 and 90203017).
文摘The silver-dppm complex, [Ag2（dppm）2（NMP）2]（SbF6）2-4H2O-3CH2Cl2 1 （NMP = 2- （4-dimethylaminophenyl）imidazo（4,5-f）（1,10）phenanthroline, dppm = diphenylphosphinomethane）, was synthesized and its structure was determined by X-ray diffraction. The crystal belongs to monoclinic, space group C2/c, Mr = 2461.61, a = 21.57（10）, b = 22.48（6）, c = 22.53（6）A, β= 101.29（2）°, V= 10713（64）A^3, Z= 4, Dc= 1.526 g/cm^3,μ= 1.141mm^-1, F（000） = 4920, R =0.0664 and wR = 0.1774 for 8524 observed reflections （1 〉 2σ（I））. Complex 1 exists as a centrosymmetric dimmer. The two dppm molecules bridge two AgNMP moieties to form an eight-membered Ag2P4C2 metallacyclic ring with ligand NMP chelating to each Ag. It appears photoluminescence （λmax = 625 nm） at room temperature and makes red shift compared with free ligand NMP （λmax = 522 nm）. DFF calculation indicates that the emission of 1 originates from singlet metal-perturbed ILCT excited state.
基金supported by the National Natural Science Foundation of China(21771021,21822501,22061130206)the Beijing Municipal Natural Science Foundation(JQ20003)+3 种基金the Newton Advanced Fellowship award(NAFR1201285)the Fok Ying-Tong Education Foundation(171008)the Measurements Fund of Beijing Normal Universitythe State Key Laboratory of Heavy Oil Processing。
文摘Three-primary-color luminescent materials are highly desirable to construct white-light emitting resource,multi-color optical displays,and tunable photonic applications.However,the efficient strategy to establish the three-primary-color systems with unique photofunctionalities is still rather limited,particularly for molecular materials.Herein,we developed a molecular cocrystal route to obtain three-primary-color emissive materials by tuning different donor-acceptor units based on the same chromophore(4,4′-bis(2,5-dimethylstyryl)biphenyl,Bdb).The warm and cold white-light together with multi-color emission in most of visible region can be highly adjusted by rationally tuning different mixture components of three-primary-color cocrystals through an energy transfer mechanism.Furthermore,the blue/green/red emitters endow Bdb molecular cocrystals novel colortunable photonic properties(such as one-dimensional(1D)/2D optical waveguide,polarized fluorescence,up-conversion luminescence,and amplified spontaneous emission),benefitting from their well-defined micro/nanostructures and high crystallinity.Particularly,the high luminescence quantum yield(82.49%)and polarized anisotropy(0.723)outperform most of state-ofthe-art molecular crystalline materials.Therefore,this work supplies an effective way to fabricate new types of three-primarycolor phosphors through luminescent cocrystals,which have promising applications in the fields of full-color displays,whitelight irradiation,low-dimensional optical polarization,and micro/nanophotonics.
基金Project supported by the German Research Foundation(DFG,research grant SE1448/7-1 for M.S.)German Academic Scholarship Foundation(Studienstiftung des deutsches Volkes,predoctoral fellowship for E.K.)。
文摘The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comparing theoretical and expe rimental electronic circular dichroism spectra.The e nantiopure cryptates exhibit strong circularly polarized luminescence with a maximum dissymmetry factor glum=0.25 for the f-f transition 5 D0→7 F1(λ=594 nm)under visible light excitation atλgx=400 nm.
