N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-prop...N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-property relationship.However,the structural type and photoresponsive application are still limited for such TOCs,especially regarding the high-nuclearity TOCs that contain structure unit of TiO_(2)for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds usingπ-conjugated 1,10-phenanthroline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti_(26)]~(2+)and half[Ti_(22)]~(2+),which renders it as the first cocrystallized TOC containing two positively charged species and phen-functionalized TOC showing the highest nuclearity up to 37 Ti centers.By adjusting the synthetic conditions,the individual{Ti_(22)}and{Ti_(26)}clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of{Ti_(22)}is mainly constructed from four lacunary{Ti_(4)}derived from pentagonal{Ti(Ti)_5}unit,while{Ti_(26)}is built from four complete{Ti(Ti)_5}unit.Notably,a{Ti_8O_(14)}structure unit of anatase TiO_(2)can be identified in{Ti_(26)}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sulfoxidation.Owing to the presence of anatase structure unit in{Ti_(26)}and the synergistic effect from{Ti_(22)}and{Ti_(26)},the catalytic performance presents in the order of Compound 1>Compound 3>Compound 2.This work provides excellent models to understand the structureproperty relationship from the perspective of cocrystallization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.展开更多
Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two...Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two cyclic TOCs are reported,namely,[Ti_(6)(μ_(3)-O)_(2)(Oi-Pr)_(8))(LA)_(2)]·i-PrOH(S1)and[Ti_(6)(μ_(3)-O)2(Oi-Pr)_(8))(LV)_(2)]·i-PrOH(S2),which are functionalized by photoactive naphthalene diimide(NDI)chromophores.Their molecular structures and photophysical and photochemical properties were systematically studied.As shown by ultraviolet-visible(UV-vis)spectra and photocurrent study results,the band gap and the photocurrent response of S1 and S2 were derived from NDI ligands which extend the absorption edge of S1 and S2 approaching 500 nm and afford high photocurrent densities of 2.12μA/cm^(2)and 1.95μA/cm^(2)for S1 and S2,respectively,demonstrating the significance of the photoactive ligand in modulating photoresponse of TOCs.This work is expected to enrich the structural library of photoactive TOCs and provide insights into understanding the structure-property relationships of sensitized clusters.展开更多
Supramolecular transformations of coordination cage or capsule have received much attention recently,which help elucidate this natural self-assembly behavior in biological systems.The current study describes the first...Supramolecular transformations of coordination cage or capsule have received much attention recently,which help elucidate this natural self-assembly behavior in biological systems.The current study describes the first supramolecular transformation of titanium-o rganic coordination capsule triggered by phenol(and H_(3) PO_(3)).The structural alterations are accompanied by the reconstruction of 5-coordinated Ti centers to 6-coordinated ones.Meanwhile,different amounts of encapsulated phenol vip molecules can be identified,dependent on the sizes of the obtained cavities.In addition,they display much better visible light absorption and air stability than the isopropanol stabilized ones.展开更多
The synthesis of titanium oxo clusters(TOCs)with both chirality and photoactivity is urgently needed to expand their applications.However,this remains a significant challenge due to synthetic difficulties and limitati...The synthesis of titanium oxo clusters(TOCs)with both chirality and photoactivity is urgently needed to expand their applications.However,this remains a significant challenge due to synthetic difficulties and limitations in chiral ligand selection.In this work,we have isolated two pairs of enantiomeric TOCs,[Ti_(3)(μ_(3)-O)(R/S-L1)_(2)(^(i)PrO)_(6)](R/S-Ti_(3);^(i)PrOH=isopropanol,R/S-L1=R/S-2'-hydroxy-[1,1'-binaphthalen]-2-yl isopropyl hydrogenphosphate)and[Ti_(4)(μ_(2)-O)(μ_(4)-O)(R/S-L2)_(2)(EtO)_(8)](R/S-Ti4;EtOH=ethanol,R/S-L2=R/S-2'-hydroxy-[1,1'-binaphthalen]-2-yl ethyl hydrogenphosphate),via an in situ ligand transformation approach.The R/S-L1 and R/S-L2 ligands were obtained by alcoholysis of R/S-L(R/S-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate)in different reaction solvents.These ligands,with additional coordination sites,facilitated the formation of novel TOCs and improved their stability.Importantly,these clusters exhibited exceptional stability in solid state and maintained appreciable stability in solution.Furthermore,the introduction of chiral ligands not only imparts a homochiral nature to R/S-Ti3 and R/S-Ti4 but also confers upon them superior photoelectric properties due to ligand-to-metal charge transfer(LMCT)phenomena,as confirmed by theoretical calculations.This study offers a valuable synthetic strategy for preparing photoactive chiral TOCs,and we anticipate it will inspire new discoveries in the field of chiral metal nanoclusters.展开更多
Compared with nanoparticle-aspect relatives titanium dioxide(TiO2),titanium-oxo clusters(TOCs)are atomically structural-determined and can be further precisely modified through coordination and supramolecular chemistr...Compared with nanoparticle-aspect relatives titanium dioxide(TiO2),titanium-oxo clusters(TOCs)are atomically structural-determined and can be further precisely modified through coordination and supramolecular chemistry.Another parallel research direction is titanium-based metal-organic frameworks,and those based on TOC have attracted particular attention because of their high optical performances resulting from the cluster aggregation effect.Though challenging,assembling macro-materials from specific clusters helps establish the assembly chemistry of clusters and incorporates porous andflexible characteristics into a single bulk material.Although separate reviews are reported in these two branches,no com-prehensive review is available to highlight the bridges between them.Herein,we review and summarize the development and progress of new aggregation of TOCs,from intramolecular unique cluster aggregation to hierarchical intermolecular aggre-gation via covalent forces,coordination bonds,and non-covalent forces using the specific clusters as precursors.We hope this reviewfills the gap in the methodology of assembling particular-aggregated TOCs and their derived frameworks,providing general guidance to researchers interested in this area.展开更多
Subject Code:B01 Photocatalytic hydrogen evolution by water-splitting has been recognized as one of the most promising solutions to the global energy and environment crisis,owing to its renewable solar energy source a...Subject Code:B01 Photocatalytic hydrogen evolution by water-splitting has been recognized as one of the most promising solutions to the global energy and environment crisis,owing to its renewable solar energy source and clean chemical fuel product.Cadmium sulfide(CdS)and TiO2(or related polyoxo-titanium clusters)are two展开更多
Titanium-based materials have emerged as promising candidates for photo-Fenton-like catalysis,whereas their structural complexities impede precise understanding of the relevant structure–activity relationships.Owing ...Titanium-based materials have emerged as promising candidates for photo-Fenton-like catalysis,whereas their structural complexities impede precise understanding of the relevant structure–activity relationships.Owing to their well-defined and tunable structures,titaniumoxo clusters appear to be facile models for looking into the photophysical and photochemical processes in Ti-H_(2)O_(2) systems.Using PTC-3 as a prototype,we interrogated the relationship between Ti-site coordination environments and photo-Fenton-like behaviors.Through integrated in-situ/exsitu spectroscopic analyses and theoretical simulations,we elucidated light-driven H_(2)O_(2) activation on hexa-coordinated and penta-coordinated Ti sites in PTC-3.The superiority of penta-coordinated Ti site was identified,where extended visible-light absorption and promoted electron transfer could synergistically boost the activation of H_(2)O_(2) into superoxide radicals.This work brightens the role of Ti-site coordination geometry in photo-Fenton-like processes and paves the way for pursuing titanium-based advanced oxidation.展开更多
通过溶剂热合成方法,以吡啶-2-甲醛肟(HPycox)和Ti(O^(i)Pr)_(4)合成了双核钛配合物[Ti_(2)(μ_(2)-O)(Pycox)_(2)(O^(i)Pr)_(4)](1)。通过结构分析,分别使用二苯基膦酸和苯基膦酸对其进行结构调控,成功制备了三核钛配合物[Ti_(3)(μ_(2...通过溶剂热合成方法,以吡啶-2-甲醛肟(HPycox)和Ti(O^(i)Pr)_(4)合成了双核钛配合物[Ti_(2)(μ_(2)-O)(Pycox)_(2)(O^(i)Pr)_(4)](1)。通过结构分析,分别使用二苯基膦酸和苯基膦酸对其进行结构调控,成功制备了三核钛配合物[Ti_(3)(μ_(2)-O)_(2)(Pycox)_(2)(Ph_(2)PO_(2))_(2)(O^(i)Pr)_(4)](2)和六核钛配合物[Ti_(6)(μ_(2)-O)_(2)(μ_(3)-O)_(2)(Pycox)_(2)(Ph PO_(3))_(4)(O^(i)Pr)_(6)]·2CH_(3)CN (3)。配合物1~3的光学带隙分别为2.89、3.00和2.87 e V,其中配合物2的光电流密度可达0.1μA·cm^(-2)。展开更多
In this work,titanium-capped cobalt clathrochelates have been applied as secondary building units(SBUs) fo r the construction of supramolecular rings.Two heterometallic wheel-like [Ti_(6) Co_(12)] complexes based on c...In this work,titanium-capped cobalt clathrochelates have been applied as secondary building units(SBUs) fo r the construction of supramolecular rings.Two heterometallic wheel-like [Ti_(6) Co_(12)] complexes based on cobalt clathrochelates,[C_(6)H_(15)N_(4)]_(2)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(2,Dmg=dimethy[glyoxime) and H_(6)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(3),have been successfully synthesized and characterized.The supramolecular stacking modes of these wheels are largely dependent on the applied synthetic conditions,which further impact their gas adsorption properties.展开更多
The construction of a thin stable shell to encapsulate perovskite with effective carrier transport is a promising strategy to fabricate highly efficient and stable perovskite based optoelectronic devices.However,it is...The construction of a thin stable shell to encapsulate perovskite with effective carrier transport is a promising strategy to fabricate highly efficient and stable perovskite based optoelectronic devices.However,it is generally difficult to control the thickness and location of the encapsulating materials,ideally on perovskite grains.In this work,we developed a one-step method for the growth of titanium alkoxide networks in-situ in perovskite film forming an encapsulating layer on perovskite nanograin homogeneously.The thin encapsulating network brings much enhanced stability and allows effective carrier transport simultaneously.Light emitting diode based on this composite shows much enhanced stability under continuous operation.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.21901037,21901038 and 92161111)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning+1 种基金the Fundamental Research Funds for the Central Universities(No.2232019G-07)the International Cooperation Fund of Science and Technology Commission of Shanghai Municipality(No.21130750100)。
文摘N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-property relationship.However,the structural type and photoresponsive application are still limited for such TOCs,especially regarding the high-nuclearity TOCs that contain structure unit of TiO_(2)for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds usingπ-conjugated 1,10-phenanthroline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti_(26)]~(2+)and half[Ti_(22)]~(2+),which renders it as the first cocrystallized TOC containing two positively charged species and phen-functionalized TOC showing the highest nuclearity up to 37 Ti centers.By adjusting the synthetic conditions,the individual{Ti_(22)}and{Ti_(26)}clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of{Ti_(22)}is mainly constructed from four lacunary{Ti_(4)}derived from pentagonal{Ti(Ti)_5}unit,while{Ti_(26)}is built from four complete{Ti(Ti)_5}unit.Notably,a{Ti_8O_(14)}structure unit of anatase TiO_(2)can be identified in{Ti_(26)}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sulfoxidation.Owing to the presence of anatase structure unit in{Ti_(26)}and the synergistic effect from{Ti_(22)}and{Ti_(26)},the catalytic performance presents in the order of Compound 1>Compound 3>Compound 2.This work provides excellent models to understand the structureproperty relationship from the perspective of cocrystallization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.
基金National Natural Science Foundation of China(Nos.92161111,21901037 and 21901038)。
文摘Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two cyclic TOCs are reported,namely,[Ti_(6)(μ_(3)-O)_(2)(Oi-Pr)_(8))(LA)_(2)]·i-PrOH(S1)and[Ti_(6)(μ_(3)-O)2(Oi-Pr)_(8))(LV)_(2)]·i-PrOH(S2),which are functionalized by photoactive naphthalene diimide(NDI)chromophores.Their molecular structures and photophysical and photochemical properties were systematically studied.As shown by ultraviolet-visible(UV-vis)spectra and photocurrent study results,the band gap and the photocurrent response of S1 and S2 were derived from NDI ligands which extend the absorption edge of S1 and S2 approaching 500 nm and afford high photocurrent densities of 2.12μA/cm^(2)and 1.95μA/cm^(2)for S1 and S2,respectively,demonstrating the significance of the photoactive ligand in modulating photoresponse of TOCs.This work is expected to enrich the structural library of photoactive TOCs and provide insights into understanding the structure-property relationships of sensitized clusters.
基金supported by the National Natural Science Foundation of China (NSFC,No.21922111)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB20000000)。
文摘Supramolecular transformations of coordination cage or capsule have received much attention recently,which help elucidate this natural self-assembly behavior in biological systems.The current study describes the first supramolecular transformation of titanium-o rganic coordination capsule triggered by phenol(and H_(3) PO_(3)).The structural alterations are accompanied by the reconstruction of 5-coordinated Ti centers to 6-coordinated ones.Meanwhile,different amounts of encapsulated phenol vip molecules can be identified,dependent on the sizes of the obtained cavities.In addition,they display much better visible light absorption and air stability than the isopropanol stabilized ones.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22325105,22201159,22171164,91961105,92361301,and 52261135637)the Natural Science Foundation of Shandong Province(Nos.ZR2021QB077 and ZR2024MB120)the Doctoral Program of Liaocheng University(No.318051944).
文摘The synthesis of titanium oxo clusters(TOCs)with both chirality and photoactivity is urgently needed to expand their applications.However,this remains a significant challenge due to synthetic difficulties and limitations in chiral ligand selection.In this work,we have isolated two pairs of enantiomeric TOCs,[Ti_(3)(μ_(3)-O)(R/S-L1)_(2)(^(i)PrO)_(6)](R/S-Ti_(3);^(i)PrOH=isopropanol,R/S-L1=R/S-2'-hydroxy-[1,1'-binaphthalen]-2-yl isopropyl hydrogenphosphate)and[Ti_(4)(μ_(2)-O)(μ_(4)-O)(R/S-L2)_(2)(EtO)_(8)](R/S-Ti4;EtOH=ethanol,R/S-L2=R/S-2'-hydroxy-[1,1'-binaphthalen]-2-yl ethyl hydrogenphosphate),via an in situ ligand transformation approach.The R/S-L1 and R/S-L2 ligands were obtained by alcoholysis of R/S-L(R/S-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate)in different reaction solvents.These ligands,with additional coordination sites,facilitated the formation of novel TOCs and improved their stability.Importantly,these clusters exhibited exceptional stability in solid state and maintained appreciable stability in solution.Furthermore,the introduction of chiral ligands not only imparts a homochiral nature to R/S-Ti3 and R/S-Ti4 but also confers upon them superior photoelectric properties due to ligand-to-metal charge transfer(LMCT)phenomena,as confirmed by theoretical calculations.This study offers a valuable synthetic strategy for preparing photoactive chiral TOCs,and we anticipate it will inspire new discoveries in the field of chiral metal nanoclusters.
基金National Natural Science Foundation of China,Grant/Award Numbers:U23A2095,22371278,92061104Science Fund for Distinguished Young Scholars of Fujian Province,Grant/Award Number:2021J06035+1 种基金Funding of Fujian Provincial Chemistry Discipline Alliance,Grant/Award Number:50025401Youth Innovation Promotion Association of the Chinese Academy of Sciences,Grant/Award Number:Y2021081。
文摘Compared with nanoparticle-aspect relatives titanium dioxide(TiO2),titanium-oxo clusters(TOCs)are atomically structural-determined and can be further precisely modified through coordination and supramolecular chemistry.Another parallel research direction is titanium-based metal-organic frameworks,and those based on TOC have attracted particular attention because of their high optical performances resulting from the cluster aggregation effect.Though challenging,assembling macro-materials from specific clusters helps establish the assembly chemistry of clusters and incorporates porous andflexible characteristics into a single bulk material.Although separate reviews are reported in these two branches,no com-prehensive review is available to highlight the bridges between them.Herein,we review and summarize the development and progress of new aggregation of TOCs,from intramolecular unique cluster aggregation to hierarchical intermolecular aggre-gation via covalent forces,coordination bonds,and non-covalent forces using the specific clusters as precursors.We hope this reviewfills the gap in the methodology of assembling particular-aggregated TOCs and their derived frameworks,providing general guidance to researchers interested in this area.
文摘Subject Code:B01 Photocatalytic hydrogen evolution by water-splitting has been recognized as one of the most promising solutions to the global energy and environment crisis,owing to its renewable solar energy source and clean chemical fuel product.Cadmium sulfide(CdS)and TiO2(or related polyoxo-titanium clusters)are two
基金supported by the National Key R&D Program of China(Nos.2022YFA1502903 and 2021YFA1501502)the National Natural Science Foundation of China(Nos.22275179 and 92477116).
文摘Titanium-based materials have emerged as promising candidates for photo-Fenton-like catalysis,whereas their structural complexities impede precise understanding of the relevant structure–activity relationships.Owing to their well-defined and tunable structures,titaniumoxo clusters appear to be facile models for looking into the photophysical and photochemical processes in Ti-H_(2)O_(2) systems.Using PTC-3 as a prototype,we interrogated the relationship between Ti-site coordination environments and photo-Fenton-like behaviors.Through integrated in-situ/exsitu spectroscopic analyses and theoretical simulations,we elucidated light-driven H_(2)O_(2) activation on hexa-coordinated and penta-coordinated Ti sites in PTC-3.The superiority of penta-coordinated Ti site was identified,where extended visible-light absorption and promoted electron transfer could synergistically boost the activation of H_(2)O_(2) into superoxide radicals.This work brightens the role of Ti-site coordination geometry in photo-Fenton-like processes and paves the way for pursuing titanium-based advanced oxidation.
文摘通过溶剂热合成方法,以吡啶-2-甲醛肟(HPycox)和Ti(O^(i)Pr)_(4)合成了双核钛配合物[Ti_(2)(μ_(2)-O)(Pycox)_(2)(O^(i)Pr)_(4)](1)。通过结构分析,分别使用二苯基膦酸和苯基膦酸对其进行结构调控,成功制备了三核钛配合物[Ti_(3)(μ_(2)-O)_(2)(Pycox)_(2)(Ph_(2)PO_(2))_(2)(O^(i)Pr)_(4)](2)和六核钛配合物[Ti_(6)(μ_(2)-O)_(2)(μ_(3)-O)_(2)(Pycox)_(2)(Ph PO_(3))_(4)(O^(i)Pr)_(6)]·2CH_(3)CN (3)。配合物1~3的光学带隙分别为2.89、3.00和2.87 e V,其中配合物2的光电流密度可达0.1μA·cm^(-2)。
基金supported by the National Natural Science Foundation of China (NSFC,Nos.21673238 and 21922111)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB20000000)。
文摘In this work,titanium-capped cobalt clathrochelates have been applied as secondary building units(SBUs) fo r the construction of supramolecular rings.Two heterometallic wheel-like [Ti_(6) Co_(12)] complexes based on cobalt clathrochelates,[C_(6)H_(15)N_(4)]_(2)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(2,Dmg=dimethy[glyoxime) and H_(6)[TiCo_(2)(μ_(2)-Oipr)(Oipr)_(2)(Dmg)_(3)]_(6)(3),have been successfully synthesized and characterized.The supramolecular stacking modes of these wheels are largely dependent on the applied synthetic conditions,which further impact their gas adsorption properties.
基金the National Key Research and Development Program of China(No.2021YFA0715502)the National Natural Science Foundation of China(Nos.61935016,92056119,22175118,and 62004125)+3 种基金Science and Technology Commission of Shanghai Municipality(Nos.20JC1415800 and 20XD1402500)the Double First-Class Initiative Fund of ShanghaiTech University and Open Research Fund of China National Key Laboratory of Materials for Integrated Circuits(No.NKLJC-K2023-04)support from Analytical Instrumentation Center(#SPST-AIC10112914),SPST,ShanghaiTech Universitythe support from Centre for High-resolution Electron Microscopy(ChEM),SPST,ShanghaiTech University under contract NO.EM02161943.
文摘The construction of a thin stable shell to encapsulate perovskite with effective carrier transport is a promising strategy to fabricate highly efficient and stable perovskite based optoelectronic devices.However,it is generally difficult to control the thickness and location of the encapsulating materials,ideally on perovskite grains.In this work,we developed a one-step method for the growth of titanium alkoxide networks in-situ in perovskite film forming an encapsulating layer on perovskite nanograin homogeneously.The thin encapsulating network brings much enhanced stability and allows effective carrier transport simultaneously.Light emitting diode based on this composite shows much enhanced stability under continuous operation.
基金the financial support from the National Key R&D Program of China(2023YFE0202500)the National Funds for Distinguished Young Scientists(61825503)+1 种基金the National Natural Science Foundation of China(22161160318 and 62275129)the Project of State Key Laboratory of Organic Electronics and Information Displays,Nanjing University of Posts&Telecommunications(GZR2023010008)。
