Spectral and photophysical investigations of 4＇-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine （APT） have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra ...Spectral and photophysical investigations of 4＇-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine （APT） have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridine nitrogen N4-NS-N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed.展开更多
Terpyridine-capped poly（ethylene glycol） （PEG） was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu（NO3）3 and the telechelic macromolecules. The structure of the complex was ch...Terpyridine-capped poly（ethylene glycol） （PEG） was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu（NO3）3 and the telechelic macromolecules. The structure of the complex was characterized by 1H NMR, FT-IR, UV-vis and fluores-cence spectroscopy. Strong fluorescent emission of the complex was observed at 593 and 616 nm upon the excitation of 300 nm. The fluo-rescent emission was quenched upon addition of trace amount of diethyl chlorophosphate （DCP）. And the observed Ksv values for DCP were measured to be 0.568×10^3 and 0.89×10^3 L/mol for quenching at 593 and 616 nm, which indicated the detection limit for DCP was about 0.014 mmol/L. These results showed that the terpyridine-lanthanide complex could be an effective chemosensor with a potential application in the detection of organophosphates.展开更多
Five organotin complexes of terpyridine derivatives were synthesized and characterized. The mononuclear Sn（IV） complexes were six-coordinated adopting a distorted octahedral coordination geometry. A brief outline of...Five organotin complexes of terpyridine derivatives were synthesized and characterized. The mononuclear Sn（IV） complexes were six-coordinated adopting a distorted octahedral coordination geometry. A brief outline of the fluorescence spectra and the in vitro cytotoxicity of the Sn（IV） complexes have been given.展开更多
A novel donor-acceptor （D-A） triphenylamino terpyridine derivative L was facilely synthesized and fully characterized, and its single crystals were obtained and determined by X-ray diffraction analysis. It crystalli...A novel donor-acceptor （D-A） triphenylamino terpyridine derivative L was facilely synthesized and fully characterized, and its single crystals were obtained and determined by X-ray diffraction analysis. It crystallizes in triclinic, space group P/ with a = 11.760（5）, b =12.516（5）, c = 12.850（5） A, α = 67.141（5）, β= 65.284（5）, γ = 75.876（5）°, Mr = 621.54, F= 1575.6（11） A3, Z= 2, Dc = 1.310 g/cm3,μ = 0.245 mm-1, F（000） = 648, the final R = 0.0671 and wR = 0.1869 for 11328 observed reflections with 1〉 2σ（I）. Linear and nonlinear optical properties of terpyridine derivative L were systematically investigated. The maximum two-photon cross-section of L was 382.5 GM （Goeppert-Mayer）, measured by two-photon excited fluorescence （TPEF） method. This result demonstrates that the increase of intramolecular charge transfer （ICT） leads to enhanced two-photon absorption （2PA）, which could be achieved by introducing additional electron-donor groups to the molecular framework.展开更多
Reactions between the 1,3-bis(6-methylpyridin-2-yl) pyridine ligand L,C17H15N3 and LnIII(1a,1b,1c,1d) or a mixture of LnIII and CuII nitrates(2a,2b,2c,2d) resulted in a series of respectively novel mono-and heterodinu...Reactions between the 1,3-bis(6-methylpyridin-2-yl) pyridine ligand L,C17H15N3 and LnIII(1a,1b,1c,1d) or a mixture of LnIII and CuII nitrates(2a,2b,2c,2d) resulted in a series of respectively novel mono-and heterodinuclea r complexes,where LnIII=Sm(a) ,Eu(b) ,Tb(c) ,Dy(d) . The compounds were char acterized by elemental analysis,ESI-MS and IR spectra,furthermore we obtained crystals of [H2L][Eu(NO3) 5](1b) and [CuL2][Eu(NO3) 5](2b) suitable for XRD char acterization. In the crystal structures the Eu ions are 10-coordinated with quit e a narrow range of Eu-O distances which are between 0.2436 and 0.2556 nm. In 1b the ligand molecule is protonated in both terminal rings,and the N-H groups ar e involved in the N-H…O hydrogen bonds with the same oxygen atom of one of the nitro groups. These hydrogen bonds connect the ions in 1b into the complex which is the principal building block of the structure. In 2b the [CuL2]2+ counterion s are present;the Cu is octahedrally coordinated by all nitrogen iatoms of two L molecules which are therefore almost perpendicular to each other. The electros tatic interactions between the charged species are in both cases the main drivin g force of the crystal packing.展开更多
A sensitive and selective zinc ion ratiometric fluorescence sensor has been synthesized and characterized. This material displays dual fluorescence. After the material was bonded to a closed-shell metal ion, such as ...A sensitive and selective zinc ion ratiometric fluorescence sensor has been synthesized and characterized. This material displays dual fluorescence. After the material was bonded to a closed-shell metal ion, such as Zn2＋, the recovery of the local excited fluorescence of the material-Zn2＋ complex, largely at the expense of the intramolecular charge transfer fluorescence, is consistent with the difference between selected orbital transitions of the free dye and the metal-chelated complex. For instance, the contribution of the πtpy→πtpy, transition becomes more prominent. This is also consistent with the results of the fluorescence decay behavior, measured via a time-correlated single photon counting setup. In contrast, the corresponding open shell Ni2＋ -bound complex quenches both kinds of photoluminescence, due to spin-orbit coupling.展开更多
A series of novel mono- and di-terpyridine derivatives with purinyl and pyrimidyl group were obtained from the reaction of 4′-p- bromomethylphenyl-2,2′：6,2″-terpyridine with 6-mercaptopurine, 2,6-dimercaptopurine ...A series of novel mono- and di-terpyridine derivatives with purinyl and pyrimidyl group were obtained from the reaction of 4′-p- bromomethylphenyl-2,2′：6,2″-terpyridine with 6-mercaptopurine, 2,6-dimercaptopurine and thymine, respectively. The active hydrogens on these alkaloids could be abstracted stepwise using different bases, which made the addition controllable.展开更多
A novel b-cyclodextrin-based terpyridine derivatives has been prepared by the coupling of 4-(4-bromomethyl phenyl)- 2, 2:6, 2-terpyridine with mono-6-hydroxy permethylated b- cyclodextrin. The cyclodextrin dimmer appe...A novel b-cyclodextrin-based terpyridine derivatives has been prepared by the coupling of 4-(4-bromomethyl phenyl)- 2, 2:6, 2-terpyridine with mono-6-hydroxy permethylated b- cyclodextrin. The cyclodextrin dimmer appending a 4-phenyl-2,2:6,2- terpyridine spacer on the primary faces was synthesized by reaction of 4-phenyl-2,2:6,2-terpyridine-6,6-dicarbonitrile with an excess of 6-deoxy-6-O-tosyl-b-cyclodextrin.展开更多
A novel terpyridine-based complex CdL＇S2 （L＇ = oxide of L; L = 10-hexyl-3-（2,6- di（pyridine-2-yl）pyridine-4-yl）-10H-phenothiazine） has been solvothermally synthesized and characterized by FT-IR spectroscopy, e...A novel terpyridine-based complex CdL＇S2 （L＇ = oxide of L; L = 10-hexyl-3-（2,6- di（pyridine-2-yl）pyridine-4-yl）-10H-phenothiazine） has been solvothermally synthesized and characterized by FT-IR spectroscopy, elemental analysis, 1HNMR and X-ray crystallography. The sulfur of phenothiazine moiety was oxidized when the crystal is formed. The complex C36H37CdN5O2S3 crystallizes in triclinic, space group P1 with a = 9.4452（9）, b = 13.0181（14）, c = 14.6721（18） A, a = 73.872（1）, β = 81.531（1）, y = 87.547（2）°, V= 1714.2（3） A3, Mr = 780.29, Dc= 1.512 g.cm-3,μ = 0.861 mm-l, F（000） = 800, Z = 2, the final R = 0.0456 and wR = 0.1059 for I 〉 2σ-（I）. The Cd（II） is coordinated by two terminal sulfur ions and three pyridyl nitrogen atoms in a distorted trigonal bipyramidal geometry. Universal hydrogen bonds between the neighboring molecules have generated a supramolecular arrangement which contributes to the stability of the title complex. Fluorescence property and thermogravimetry of the complex have also been investigated and discussed.展开更多
Two novel mono-nuclear zinc（Ⅱ） complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis （EA） and X-ray Diffraction （XRD）. The UV-vis...Two novel mono-nuclear zinc（Ⅱ） complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis （EA） and X-ray Diffraction （XRD）. The UV-vis spectra show the ligand-centered （LC） π-π＊ transitions and intra-ligand charge transfer （1ILCT） transitions,and the 1ILCT band red-shifts with the increasing number of aromatic amine groups in the ligands. Complex [Zn（L1）2]（PF6）2 with an aromatic amine group in ligand shows a strong emission peak at 523 nm in the MeCN solution at 293 K and a blue-shifted band at 517 nm in the alcoholic glass at 77 K. However,for complex [Zn（L2）2]（PF6）2 containing aniline dimer modified ligand,no apparent emission can be observed in the MeCN solution at room temperature due to a PET non-radiative decay pathway. Both of them show multiplicate redox processes based on oligoaniline and terpyridine units. The shifts of redox potentials also reflect the D-A interactions between the oligoaniline units and [Zn（TPY）2]2＋ core.展开更多
The condensation reaction ofω-aminoalkyleneamide-functionalized pillar[5]arenes with 2-(4-([2,2’:6’,2〃-terpyridin]-4’-yl)phenoxy)acetic acid or 4-(4-([2,2’:6’,2"-terpyridin]-4’-yl)phenoxy)butanoic acid in...The condensation reaction ofω-aminoalkyleneamide-functionalized pillar[5]arenes with 2-(4-([2,2’:6’,2〃-terpyridin]-4’-yl)phenoxy)acetic acid or 4-(4-([2,2’:6’,2"-terpyridin]-4’-yl)phenoxy)butanoic acid in dry chloroform at room temperature under the catalysis of HOBT/EDCl resulted in novel pillar[5]arene diamido-bridged terpyridine derivatives.~1 H NMR and 2 D NOESY spectra clearly indicated that the interesting[1]rotaxanes were formed by longer alkylene such as propylene,butylene and hexylenediamido chains threading into the cavity of the pillar[5]arene and with larger terpyridine acting as the stopper.However,the shorter ethylenediamido chain only exists outer of cavity of pillar[5]arene and the molecule exist on free form.展开更多
The title compound, [Zn（4-pytpy）（NO3）2] （4-pytpy = 4′-（4-pyridyl）-2,2′：6′,2＂- terpyridine） 1, has been synthesized by the solvothermal reaction of Zn（NO3）2·6H2O with 4-pytpy in CH3OH solution. It c...The title compound, [Zn（4-pytpy）（NO3）2] （4-pytpy = 4′-（4-pyridyl）-2,2′：6′,2＂- terpyridine） 1, has been synthesized by the solvothermal reaction of Zn（NO3）2·6H2O with 4-pytpy in CH3OH solution. It crystallizes in the triclinic system, space group P1 with a = 8.358（6）, b = 11.121（8）, c = 11.374（8）A, α = 74.226（11）, β = 74.532（11）, γ = 83.085（12）°, Mr= 499.74, V= 979.3（12） A3, Z = 2, Dc = 1.695 g/cm3, F（000） = 508,μ = 1.309 mm^-1, the final R = 0.0547 and wR = 0.1588. X-ray crystal structure analysis revealed that the Znn is hexa-eoordinated by two oxygen atoms from two nitrate groups and four nitrogen atoms, three of which are from the tridentate domain of one 4-pytpy and the other from the monodentate domain of another 4-pytpy. 4-pytpy as a bridging ligand connects ZnⅡ into a one-dimensional coordination polymer.展开更多
We have succeeded in causing reversible polymorphic transformation of 2,2':6',2"-terpyridine (terpy). By contacting a template terpy crystal with the target crystal, reversible orthorhombic-to-monoclinic ...We have succeeded in causing reversible polymorphic transformation of 2,2':6',2"-terpyridine (terpy). By contacting a template terpy crystal with the target crystal, reversible orthorhombic-to-monoclinic transformation occurred directly without via melting state. The transformation process is successfully visualized and it is found that the template crystal influences the transition temperature itself.展开更多
New type of photoluminescence properties of 2,2’:6’,2”-Terpyridine (Terpy) is described. Orthorhombic form of Terpy crystals, which is known to be inherently nonluminous in the visible region, was found to emit str...New type of photoluminescence properties of 2,2’:6’,2”-Terpyridine (Terpy) is described. Orthorhombic form of Terpy crystals, which is known to be inherently nonluminous in the visible region, was found to emit strong green light in the presence of traces amount of impurities. Hydroxy-terpyridine, originally included in the Terpy reagent, was found to be the main cause of the green luminescence. Tuning of the luminescent color is possible depending on the dopant species.展开更多
In summary,a novel structure of MOF based on 1,4-di([2,2':6',2''terpyridin]-4'-yl)benzene and 1,4-naphthalenedicarboxylic acid has been constructed through hydrothermal reaction.The Ni-MOF displays...In summary,a novel structure of MOF based on 1,4-di([2,2':6',2''terpyridin]-4'-yl)benzene and 1,4-naphthalenedicarboxylic acid has been constructed through hydrothermal reaction.The Ni-MOF displays one dimensional zigzag chain,which connect each other by hydrogen bonding to form three dimensional supramolecule with large channels.The conjugated systems of the terpyridin and benzene ligands enhance the chain rigidity,accelerate the electron transport.The massive channels provides electrolyte rapid transfer.By the structural feature aforementioned,the Ni-MOF demonstrates stable electrochemical performance as suprocapacitor.展开更多
The G-quartet,a hydrogen-bonded macrocycle formed by cation-templated assembly of guanosine derivative,plays a vital role in areas ranging from structural biology to supramolecular chemistry and nanotechnology.Herein,...The G-quartet,a hydrogen-bonded macrocycle formed by cation-templated assembly of guanosine derivative,plays a vital role in areas ranging from structural biology to supramolecular chemistry and nanotechnology.Herein,we show a zinc-terpyridine derivative(Ftpy)that could form complex with various guanosine phosphates,exhibiting relatively weak circularly polarized luminescence CPL(dissymmetry factor,glum≈1×10^(-3)).Interestingly,when Ag^(+)ions are involved,significantly boosted circularly polarized luminescence(CPL)is obtained in the assemblies of Ftpy with GTP,which the glum can reach to 0.15.In contrast,no significant difference is observed in the presence of other cations(Na^(+),K^(+),Rb^(+),NH_(4)^(+),Cu^(2+),and Sr^(2+)).It reveals that CPL signal is amplified due to the formation of G-quartet in the presence of Ag^(+)ions,which further hierarchically self-associate into helically stacked supramolecular aggregates with the cooperation andπ-πof Ftpy,contributing to the expression of chirality information.Furthermore,the co-assemblies of Ftpy/GTP/Ag^(+)exhibit an enantioselective recognition of enantiomeric penicillamine by CPL spectra.This work provides a straightforward avenue to fabricate supramolecular assemblies with strong CPL based on G-quartet formation.展开更多
The development of artificial supramolecular double-stranded helical structures has received widespread attention;however,the reports focusing on the construction and resolution of double-stranded helical assemblies b...The development of artificial supramolecular double-stranded helical structures has received widespread attention;however,the reports focusing on the construction and resolution of double-stranded helical assemblies based on terpyridine are relatively scarce.Herein,we report a series of extremely low-symmetry double-stranded helicates(S^(3),S^(4),and S^(R/S))based on the head-totail coordination mode of ladder-style ligands(L^(3),L^(4),and LR/S),which are apparently different from the conventional helicates with symmetrical axis.The ladder-style tridentate ligand L^(3)was first designed and synthesized by characteristic consecutive unsymmetrical modification of terpyridine.The chiral group 2,6-bis(oxazolinyl)pyridine(Py Box)was designed at the tail of tridentate ligand L^(3)and achieved the chiral resolution of the assembly.Moreover,the self-assembly of mixed three ladder-style ligands(didentate L2,tridentate L^(3),and tetradentate L^(4))and single terpyridine ligand(L^(1))with Zn(Ⅱ)also exhibited excellent narcissistic self-sorting behavior,without any statistical mixture.展开更多
Polyoxometalates modified with complex cations have attracted increasing attention because of the fascinating properties and the controllable structures.By adjusting the synthesis conditions,four new terpyridine compl...Polyoxometalates modified with complex cations have attracted increasing attention because of the fascinating properties and the controllable structures.By adjusting the synthesis conditions,four new terpyridine complexes based hybrid POMs,[(TPY-H)CuCl]_(4)[W_(10)O_(32)]·2DMF·2H_(2)O(1),[(TPY-H)Cu(DMSO)(H_(2)O)]_(2)[W_(10)O_(32)]·2H_(2)O(2),[(TPY-H)_(2)Cu]_(2)[W_(10)O_(32)]·6DMSO·8H_(2)O(3) and[(TPY-Br)CuCl(DMSO)(H_(2)O)]_(2)[(TPY-Br)CuCl]_(2)[W_(10)O_(32)]·2DMSO·4H_(2)O(4),were prepared by using‘one-pot’method.Sing-crystal X-ray diffraction analyses,infrared radiation,etc.,revealed the structural composition of compounds 1—4,which indicates that synthesis conditions have a directional regulatory effect on the compounds synthesis.Thioether oxidation catalytic reactions show 1—4 have good catalytic activities,and powder X-ray diffraction and thermogravimetry analysis show 1—4 have superduper catalytic stability.Moreover,4 has better catalytic activity because of the different structure of terpyridine complexes.Therefore,a possible mechanism of dual-site catalysis by both cations and anions is proposed.展开更多
The electron-donating unit 2,3,4,6-tetrahydro-1,6-dithia-3a-azaphenalene (THDTAP) was introduced onto terpyridine (TPy) to give a donor-acceptor (D-A) type TPy-ligand (compound 2).Upon selective oxidation of two sulfu...The electron-donating unit 2,3,4,6-tetrahydro-1,6-dithia-3a-azaphenalene (THDTAP) was introduced onto terpyridine (TPy) to give a donor-acceptor (D-A) type TPy-ligand (compound 2).Upon selective oxidation of two sulfur atoms on the THDTAP moiety of 2,the ligands 3-6 were created.The electronic structures of 2-6 were evaluated by theoretical,electrochemical,and spectroscopic investigations.The oxidation on the sulfur atoms brings significant influence on the electron-donating ability of THDTAP moiety,subsequently,leads to fine modulations on intramolecular charge-transfer (ICT) of 2-6 and the electronically excited states of the complexes of 2-6 with metal ions.Based on the optical response of 2-6 toward metal ions,the step-by-step recognition of Zn2+,Cd2+,and Ag+ ions is set up by employing 2 and 3 as combined fluorescence sensors.展开更多
Two novel terpyridine-based chromophores with D-A (D = donor, A = acceptor) structural model containing modified triphenylamine moiety (L1 and L2 ) have been conveniently synthesized via formylation and reduction in s...Two novel terpyridine-based chromophores with D-A (D = donor, A = acceptor) structural model containing modified triphenylamine moiety (L1 and L2 ) have been conveniently synthesized via formylation and reduction in satisfactory yields, and fully characterized. The single crystals of them were obtained and determined by X-ray diffraction analysis. The relationships between structure and photophysical properties of the two chromophores were investigated both experimentally and theoretically. The measured maximum TPA cross-sections per molecular weight (δmax /MW) of the chromophores are 0.63 GM/(g mol) (L1) and 0.72 GM/(g mol) (L2), respectively, in DMF as a high polar solvent. The results indicate that the value of δmax/MW could be well tuned by the intramolecular charge transfer (ICT), which could be realized by introducing additional elecron-donor/acceptor groups.展开更多
文摘Spectral and photophysical investigations of 4＇-（p-aminophenyl）-2,2＇：6＇,2″-terpyridine （APT） have been performed in various solvents with different polarity and hydrogen-bonding ability. The emission spectra of APT are found to exhibit dual fluorescence in polar solvents, which attributes to the local excited and intramolecular charge transfer states, respectively. The two-state model is proven out for APT in polar solvent by the time-correlated single photon counting emission decay measurement. Interestingly, the linear relationships of different emission maxima and solvent polarity parameter are found for APT in protic and aprotic solvents, because of the hydrogen bond formation between APT and alcohols at the amino nitrogen N25. Furthermore, the effects of the complexation of the metal ion with tpy group of APT and the hydrogen bond formation between APT with methanol at the terpyridine nitrogen N4-NS-N14 are also presented. The appearance of new long-wave absorption and fluorescence bands indicates that a new ground state of the complexes is formed.
基金Project supported by Research Foundation of the General Armament Department (2008CD012)
文摘Terpyridine-capped poly（ethylene glycol） （PEG） was synthesized as a novel polymeric ligand and rare earth complex was prepared from Eu（NO3）3 and the telechelic macromolecules. The structure of the complex was characterized by 1H NMR, FT-IR, UV-vis and fluores-cence spectroscopy. Strong fluorescent emission of the complex was observed at 593 and 616 nm upon the excitation of 300 nm. The fluo-rescent emission was quenched upon addition of trace amount of diethyl chlorophosphate （DCP）. And the observed Ksv values for DCP were measured to be 0.568×10^3 and 0.89×10^3 L/mol for quenching at 593 and 616 nm, which indicated the detection limit for DCP was about 0.014 mmol/L. These results showed that the terpyridine-lanthanide complex could be an effective chemosensor with a potential application in the detection of organophosphates.
基金the financial supports from the Natural Science Foundation of China(No.21101069)
文摘Five organotin complexes of terpyridine derivatives were synthesized and characterized. The mononuclear Sn（IV） complexes were six-coordinated adopting a distorted octahedral coordination geometry. A brief outline of the fluorescence spectra and the in vitro cytotoxicity of the Sn（IV） complexes have been given.
基金supported by the National Natural Science Foundation of China(51372003)Natural Science Foundation of Anhui Province(1208085MB22)Natural Science Foundation of Fuyang Normal School(2014FSKJ07)
文摘A novel donor-acceptor （D-A） triphenylamino terpyridine derivative L was facilely synthesized and fully characterized, and its single crystals were obtained and determined by X-ray diffraction analysis. It crystallizes in triclinic, space group P/ with a = 11.760（5）, b =12.516（5）, c = 12.850（5） A, α = 67.141（5）, β= 65.284（5）, γ = 75.876（5）°, Mr = 621.54, F= 1575.6（11） A3, Z= 2, Dc = 1.310 g/cm3,μ = 0.245 mm-1, F（000） = 648, the final R = 0.0671 and wR = 0.1869 for 11328 observed reflections with 1〉 2σ（I）. Linear and nonlinear optical properties of terpyridine derivative L were systematically investigated. The maximum two-photon cross-section of L was 382.5 GM （Goeppert-Mayer）, measured by two-photon excited fluorescence （TPEF） method. This result demonstrates that the increase of intramolecular charge transfer （ICT） leads to enhanced two-photon absorption （2PA）, which could be achieved by introducing additional electron-donor groups to the molecular framework.
基金Project support by the Polish Ministry of Higher Education and Science (NN 204 2716 33)
文摘Reactions between the 1,3-bis(6-methylpyridin-2-yl) pyridine ligand L,C17H15N3 and LnIII(1a,1b,1c,1d) or a mixture of LnIII and CuII nitrates(2a,2b,2c,2d) resulted in a series of respectively novel mono-and heterodinuclea r complexes,where LnIII=Sm(a) ,Eu(b) ,Tb(c) ,Dy(d) . The compounds were char acterized by elemental analysis,ESI-MS and IR spectra,furthermore we obtained crystals of [H2L][Eu(NO3) 5](1b) and [CuL2][Eu(NO3) 5](2b) suitable for XRD char acterization. In the crystal structures the Eu ions are 10-coordinated with quit e a narrow range of Eu-O distances which are between 0.2436 and 0.2556 nm. In 1b the ligand molecule is protonated in both terminal rings,and the N-H groups ar e involved in the N-H…O hydrogen bonds with the same oxygen atom of one of the nitro groups. These hydrogen bonds connect the ions in 1b into the complex which is the principal building block of the structure. In 2b the [CuL2]2+ counterion s are present;the Cu is octahedrally coordinated by all nitrogen iatoms of two L molecules which are therefore almost perpendicular to each other. The electros tatic interactions between the charged species are in both cases the main drivin g force of the crystal packing.
基金Supported by the National Natural Science Foundation of China(Nos20633070, 20833008)the National Key Basic Research Special Foundation of China(Nos2007CB815202)
文摘A sensitive and selective zinc ion ratiometric fluorescence sensor has been synthesized and characterized. This material displays dual fluorescence. After the material was bonded to a closed-shell metal ion, such as Zn2＋, the recovery of the local excited fluorescence of the material-Zn2＋ complex, largely at the expense of the intramolecular charge transfer fluorescence, is consistent with the difference between selected orbital transitions of the free dye and the metal-chelated complex. For instance, the contribution of the πtpy→πtpy, transition becomes more prominent. This is also consistent with the results of the fluorescence decay behavior, measured via a time-correlated single photon counting setup. In contrast, the corresponding open shell Ni2＋ -bound complex quenches both kinds of photoluminescence, due to spin-orbit coupling.
基金the Natural Science Foundation for colleges and University in Jiangsu province (No.07KJD320013)the Natural Science Foundation of Huaihai Institute of Technologe(Nos.Z2006006,Z2007043)for financial support.
文摘A series of novel mono- and di-terpyridine derivatives with purinyl and pyrimidyl group were obtained from the reaction of 4′-p- bromomethylphenyl-2,2′：6,2″-terpyridine with 6-mercaptopurine, 2,6-dimercaptopurine and thymine, respectively. The active hydrogens on these alkaloids could be abstracted stepwise using different bases, which made the addition controllable.
基金This work was supported by the Natural Science Foundation of Guangxi Province(No.0135009)the Youth Foundation of Guangxi University for Nationalities.
文摘A novel b-cyclodextrin-based terpyridine derivatives has been prepared by the coupling of 4-(4-bromomethyl phenyl)- 2, 2:6, 2-terpyridine with mono-6-hydroxy permethylated b- cyclodextrin. The cyclodextrin dimmer appending a 4-phenyl-2,2:6,2- terpyridine spacer on the primary faces was synthesized by reaction of 4-phenyl-2,2:6,2-terpyridine-6,6-dicarbonitrile with an excess of 6-deoxy-6-O-tosyl-b-cyclodextrin.
基金Supported by the National Natural Science Foundation of China(201101001,21071001,50873001)the Natural Science FoundationScientific Innovation Team Foundation of Education Department of Anhui Province(KJ2012A025,KJ2010A030,2006KJ007TD)
文摘A novel terpyridine-based complex CdL＇S2 （L＇ = oxide of L; L = 10-hexyl-3-（2,6- di（pyridine-2-yl）pyridine-4-yl）-10H-phenothiazine） has been solvothermally synthesized and characterized by FT-IR spectroscopy, elemental analysis, 1HNMR and X-ray crystallography. The sulfur of phenothiazine moiety was oxidized when the crystal is formed. The complex C36H37CdN5O2S3 crystallizes in triclinic, space group P1 with a = 9.4452（9）, b = 13.0181（14）, c = 14.6721（18） A, a = 73.872（1）, β = 81.531（1）, y = 87.547（2）°, V= 1714.2（3） A3, Mr = 780.29, Dc= 1.512 g.cm-3,μ = 0.861 mm-l, F（000） = 800, Z = 2, the final R = 0.0456 and wR = 0.1059 for I 〉 2σ-（I）. The Cd（II） is coordinated by two terminal sulfur ions and three pyridyl nitrogen atoms in a distorted trigonal bipyramidal geometry. Universal hydrogen bonds between the neighboring molecules have generated a supramolecular arrangement which contributes to the stability of the title complex. Fluorescence property and thermogravimetry of the complex have also been investigated and discussed.
基金Supported by the Natural Science Foundation of Henan Province (No. 102300410221)the Natural Science Foundation of Nanyang Normal University (No. ZX2010012)Project supported by the Young Core Instructor from the Education Commission of Henan Province
文摘Two novel mono-nuclear zinc（Ⅱ） complexes with oligoaniline-functionalized terpyridine ligands have been synthesized and verified by 1H-NMR,13C-NMR,Elemental Analysis （EA） and X-ray Diffraction （XRD）. The UV-vis spectra show the ligand-centered （LC） π-π＊ transitions and intra-ligand charge transfer （1ILCT） transitions,and the 1ILCT band red-shifts with the increasing number of aromatic amine groups in the ligands. Complex [Zn（L1）2]（PF6）2 with an aromatic amine group in ligand shows a strong emission peak at 523 nm in the MeCN solution at 293 K and a blue-shifted band at 517 nm in the alcoholic glass at 77 K. However,for complex [Zn（L2）2]（PF6）2 containing aniline dimer modified ligand,no apparent emission can be observed in the MeCN solution at room temperature due to a PET non-radiative decay pathway. Both of them show multiplicate redox processes based on oligoaniline and terpyridine units. The shifts of redox potentials also reflect the D-A interactions between the oligoaniline units and [Zn（TPY）2]2＋ core.
基金financially supported by the National Natural Science Foundation of China (No.21871227)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The condensation reaction ofω-aminoalkyleneamide-functionalized pillar[5]arenes with 2-(4-([2,2’:6’,2〃-terpyridin]-4’-yl)phenoxy)acetic acid or 4-(4-([2,2’:6’,2"-terpyridin]-4’-yl)phenoxy)butanoic acid in dry chloroform at room temperature under the catalysis of HOBT/EDCl resulted in novel pillar[5]arene diamido-bridged terpyridine derivatives.~1 H NMR and 2 D NOESY spectra clearly indicated that the interesting[1]rotaxanes were formed by longer alkylene such as propylene,butylene and hexylenediamido chains threading into the cavity of the pillar[5]arene and with larger terpyridine acting as the stopper.However,the shorter ethylenediamido chain only exists outer of cavity of pillar[5]arene and the molecule exist on free form.
基金Supported by the Cultivation Fund of the Key Scientific and Technical Innovation Project,Ministry of Education of China(No.708084) the Opening Project of Key Laboratory of Synthetic and Natural Functional Molecule Chemistry(Northwest University),Ministry of Education
文摘The title compound, [Zn（4-pytpy）（NO3）2] （4-pytpy = 4′-（4-pyridyl）-2,2′：6′,2＂- terpyridine） 1, has been synthesized by the solvothermal reaction of Zn（NO3）2·6H2O with 4-pytpy in CH3OH solution. It crystallizes in the triclinic system, space group P1 with a = 8.358（6）, b = 11.121（8）, c = 11.374（8）A, α = 74.226（11）, β = 74.532（11）, γ = 83.085（12）°, Mr= 499.74, V= 979.3（12） A3, Z = 2, Dc = 1.695 g/cm3, F（000） = 508,μ = 1.309 mm^-1, the final R = 0.0547 and wR = 0.1588. X-ray crystal structure analysis revealed that the Znn is hexa-eoordinated by two oxygen atoms from two nitrate groups and four nitrogen atoms, three of which are from the tridentate domain of one 4-pytpy and the other from the monodentate domain of another 4-pytpy. 4-pytpy as a bridging ligand connects ZnⅡ into a one-dimensional coordination polymer.
文摘We have succeeded in causing reversible polymorphic transformation of 2,2':6',2"-terpyridine (terpy). By contacting a template terpy crystal with the target crystal, reversible orthorhombic-to-monoclinic transformation occurred directly without via melting state. The transformation process is successfully visualized and it is found that the template crystal influences the transition temperature itself.
文摘New type of photoluminescence properties of 2,2’:6’,2”-Terpyridine (Terpy) is described. Orthorhombic form of Terpy crystals, which is known to be inherently nonluminous in the visible region, was found to emit strong green light in the presence of traces amount of impurities. Hydroxy-terpyridine, originally included in the Terpy reagent, was found to be the main cause of the green luminescence. Tuning of the luminescent color is possible depending on the dopant species.
基金This work was financially supported by the National Natural Science Foundation of China(22209037)the Fundamental Research Funds for the Central Universities(No.B220202042).
文摘In summary,a novel structure of MOF based on 1,4-di([2,2':6',2''terpyridin]-4'-yl)benzene and 1,4-naphthalenedicarboxylic acid has been constructed through hydrothermal reaction.The Ni-MOF displays one dimensional zigzag chain,which connect each other by hydrogen bonding to form three dimensional supramolecule with large channels.The conjugated systems of the terpyridin and benzene ligands enhance the chain rigidity,accelerate the electron transport.The massive channels provides electrolyte rapid transfer.By the structural feature aforementioned,the Ni-MOF demonstrates stable electrochemical performance as suprocapacitor.
基金supported by the National Natural Science Foundation of China(92356302,52321006)the CAS Project for Young Scientists in Basic Research(YSBR-027)the China Postdoctoral Science Foundation(GZC20240391,2024M750761).
文摘The G-quartet,a hydrogen-bonded macrocycle formed by cation-templated assembly of guanosine derivative,plays a vital role in areas ranging from structural biology to supramolecular chemistry and nanotechnology.Herein,we show a zinc-terpyridine derivative(Ftpy)that could form complex with various guanosine phosphates,exhibiting relatively weak circularly polarized luminescence CPL(dissymmetry factor,glum≈1×10^(-3)).Interestingly,when Ag^(+)ions are involved,significantly boosted circularly polarized luminescence(CPL)is obtained in the assemblies of Ftpy with GTP,which the glum can reach to 0.15.In contrast,no significant difference is observed in the presence of other cations(Na^(+),K^(+),Rb^(+),NH_(4)^(+),Cu^(2+),and Sr^(2+)).It reveals that CPL signal is amplified due to the formation of G-quartet in the presence of Ag^(+)ions,which further hierarchically self-associate into helically stacked supramolecular aggregates with the cooperation andπ-πof Ftpy,contributing to the expression of chirality information.Furthermore,the co-assemblies of Ftpy/GTP/Ag^(+)exhibit an enantioselective recognition of enantiomeric penicillamine by CPL spectra.This work provides a straightforward avenue to fabricate supramolecular assemblies with strong CPL based on G-quartet formation.
基金supported by the Natural Science Foundation of Jilin Province(20230101027JC for M.Wang)the National Natural Science Foundation of China(22071079 for M.Wang)the Natural Science Foundation of Xinjiang Uygur Autonomous Region(2023D01C203 for J.Ma)。
文摘The development of artificial supramolecular double-stranded helical structures has received widespread attention;however,the reports focusing on the construction and resolution of double-stranded helical assemblies based on terpyridine are relatively scarce.Herein,we report a series of extremely low-symmetry double-stranded helicates(S^(3),S^(4),and S^(R/S))based on the head-totail coordination mode of ladder-style ligands(L^(3),L^(4),and LR/S),which are apparently different from the conventional helicates with symmetrical axis.The ladder-style tridentate ligand L^(3)was first designed and synthesized by characteristic consecutive unsymmetrical modification of terpyridine.The chiral group 2,6-bis(oxazolinyl)pyridine(Py Box)was designed at the tail of tridentate ligand L^(3)and achieved the chiral resolution of the assembly.Moreover,the self-assembly of mixed three ladder-style ligands(didentate L2,tridentate L^(3),and tetradentate L^(4))and single terpyridine ligand(L^(1))with Zn(Ⅱ)also exhibited excellent narcissistic self-sorting behavior,without any statistical mixture.
基金the support from the Project Foundation of Hunan Provincial Education Department(21C1642,22B0641,21B0584)the Research project of Changsha Normal University(XJYB202103)+1 种基金the Natural Science Foundation of Hunan Province(2023JJ40235)the National Natural Science Foundation of China(22204050).
文摘Polyoxometalates modified with complex cations have attracted increasing attention because of the fascinating properties and the controllable structures.By adjusting the synthesis conditions,four new terpyridine complexes based hybrid POMs,[(TPY-H)CuCl]_(4)[W_(10)O_(32)]·2DMF·2H_(2)O(1),[(TPY-H)Cu(DMSO)(H_(2)O)]_(2)[W_(10)O_(32)]·2H_(2)O(2),[(TPY-H)_(2)Cu]_(2)[W_(10)O_(32)]·6DMSO·8H_(2)O(3) and[(TPY-Br)CuCl(DMSO)(H_(2)O)]_(2)[(TPY-Br)CuCl]_(2)[W_(10)O_(32)]·2DMSO·4H_(2)O(4),were prepared by using‘one-pot’method.Sing-crystal X-ray diffraction analyses,infrared radiation,etc.,revealed the structural composition of compounds 1—4,which indicates that synthesis conditions have a directional regulatory effect on the compounds synthesis.Thioether oxidation catalytic reactions show 1—4 have good catalytic activities,and powder X-ray diffraction and thermogravimetry analysis show 1—4 have superduper catalytic stability.Moreover,4 has better catalytic activity because of the different structure of terpyridine complexes.Therefore,a possible mechanism of dual-site catalysis by both cations and anions is proposed.
基金The authors ack no wledge the grant from the Nati onal Natural Science Foundation of China (Nos. 21871119, 21522203)the National Key R&D Program of China (No. 2017YFA0204903).
文摘The electron-donating unit 2,3,4,6-tetrahydro-1,6-dithia-3a-azaphenalene (THDTAP) was introduced onto terpyridine (TPy) to give a donor-acceptor (D-A) type TPy-ligand (compound 2).Upon selective oxidation of two sulfur atoms on the THDTAP moiety of 2,the ligands 3-6 were created.The electronic structures of 2-6 were evaluated by theoretical,electrochemical,and spectroscopic investigations.The oxidation on the sulfur atoms brings significant influence on the electron-donating ability of THDTAP moiety,subsequently,leads to fine modulations on intramolecular charge-transfer (ICT) of 2-6 and the electronically excited states of the complexes of 2-6 with metal ions.Based on the optical response of 2-6 toward metal ions,the step-by-step recognition of Zn2+,Cd2+,and Ag+ ions is set up by employing 2 and 3 as combined fluorescence sensors.
基金the National Natural Science Foundation of China (21071001, 51142011, 21271004, 21201005 and 21271003)Ministry of Education Funded Projects Focus on returned overseas scholarProgram for New Century Excellent Talents in University (China)
文摘Two novel terpyridine-based chromophores with D-A (D = donor, A = acceptor) structural model containing modified triphenylamine moiety (L1 and L2 ) have been conveniently synthesized via formylation and reduction in satisfactory yields, and fully characterized. The single crystals of them were obtained and determined by X-ray diffraction analysis. The relationships between structure and photophysical properties of the two chromophores were investigated both experimentally and theoretically. The measured maximum TPA cross-sections per molecular weight (δmax /MW) of the chromophores are 0.63 GM/(g mol) (L1) and 0.72 GM/(g mol) (L2), respectively, in DMF as a high polar solvent. The results indicate that the value of δmax/MW could be well tuned by the intramolecular charge transfer (ICT), which could be realized by introducing additional elecron-donor/acceptor groups.
