Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 27
Filter
Add more filters










Publication year range
1.
Dalton Trans ; 50(11): 3916-3922, 2021 Mar 21.
Article in English | MEDLINE | ID: mdl-33635301

ABSTRACT

Three AIE (aggregation-induced emission)-ESIPT (excited-state intramolecular proton transfer) active 2-(2-hydroxyphenyl)benzothiazole derivatives, HL1, HL2 and HL3 with one, two and three rotatable phenyl groups, were obtained and characterized. Their AIE properties in THF/HEPES solution were investigated in detail. HL2 shows the best AIE performance with 71-fold fluorescence enhancement, while HL3 only shows a 9-fold enhancement. With the AIE property, HL1 and HL2 could act as fluorescence chemosensors to detect Cu2+ ions via the "turn off" mode in THF/HEPES media. With the ESIPT property, HL1 and HL2 could also detect Zn2+ ions via the "turn on" mode in EtOH/HEPES media. During the detection process, both demonstrate rapid response and high contrast before and after the addition of metal ions. The species formed in the detection system were investigated. The results of X-ray single-crystal diffraction confirm that Zn2+ is coordinated with the oxygen atom and Schiff base nitrogen atom instead of the benzothiazole nitrogen atom in the tetrahedron geometry. Moreover, the chemosensors were successfully constructed into handy fluorescence test papers for Cu2+ and Zn2+ detection.

2.
Dalton Trans ; 50(4): 1507-1513, 2021 Feb 07.
Article in English | MEDLINE | ID: mdl-33443271

ABSTRACT

A multi-binding site chemosensor, N-(3-methoxy-2-hydroxybenzylidene)-3-hydroxy-2-naphthahydrazone (H3L), with excited-state intramolecular proton transfer (ESIPT) behaviour was prepared and characterized. It possesses no aggregation-induced emission (AIE) characteristics but can detect Cd2+ and Zn2+ ions selectively in the "off-on" mode based on the AIE of their complexes in the media of THF/HEPES and THF/H2O, respectively, which will provide a new strategy for target detection based on AIE. The detection limits of Zn2+ and Cd2+ were 9.85 × 10-9 M and 1.27 × 10-7 M, respectively. The aggregates of the complexes formed in the detection system were confirmed by DLS data and SEM images. The corresponding Zn2+ (1) and Cd2+ (2) complexes were prepared to investigate the response mechanism. Powder X-ray diffraction and single crystal X-ray diffraction proved that complex 1 is the species formed in the detection system. The chemosensor coordinates with the Cd2+ and Zn2+ ions in different formation and coordination modes, leading to the emission position of the aggregates at 560 and 645 nm, respectively, based on which Cd2+ ions were successfully differentiated from Zn2+ ions. Moreover, the detection of Cd2+ and Zn2+ ions was realized qualitatively via test paper and quantitatively in water.

3.
Inorg Chem ; 58(7): 4626-4633, 2019 Apr 01.
Article in English | MEDLINE | ID: mdl-30869518

ABSTRACT

We first report single crystal X-ray analysis of ground crystals of mechanochromic luminescence (MCL) that shows single crystal-to-single crystal transformation (SCSCT). Single crystals of [ZnL2] (1-SG, HL = 2-[[[4-(2-benzoxazolyl)phenyl]imino]-methyl]-5-(diethylamino)-phenol) were obtained upon slight grinding of single crystals of [ZnL2]·0.5CH3OH (1), both of which were characterized by single crystal X-ray diffraction. Crystals of 1 showed emission centered at 647 nm (red color), while crystals of 1-SG showed emission band at 624 nm (orange-red color) under UV light, indicating MCL property of the Zn(II) complex. Reversible MCL property with emission color change between red and yellow for 1 was observed upon high grinding and recrystallization. Single crystal X-ray analysis suggested that it is due to the alteration of molecular conformation of ligands in ZnL2 instead of weak intermolecular interaction that 1 exhibits MCL. Investigation of the control Zn(II) complexes (2-4) indicated that flexible substituents and rotated aromatic rings are desirable to generate the MCL-active complexes. In addition, 1 was highly fluorescent in THF solution, but its fluorescence quenched upon addition of water. DFT calculations suggested that this is due to the formation of the excited hydrated ZnL2 species via Zn-O coordination bond, which results in electron-driven proton transfer (EDPT). Aggregates formed as water fraction ( fw) in THF/H2O (v/v) reached 70%, and fluorescence emission was enhanced. This phenomenon continued until fw was 90%, indicating aggregation-induced emission (AIE) property. The mechanism of AIE of ZnL2 in THF/H2O is the restriction of intramolecular rotation (RIR).

4.
Dalton Trans ; 47(38): 13730-13738, 2018 Oct 02.
Article in English | MEDLINE | ID: mdl-30215083

ABSTRACT

A D-π-A Schiff-base compound, 2-amino-3({[4-(diethylamino)-2-hydroxylphenyl]methylene}amino)-but-2-enedinitrile (H2L), was prepared using diaminomaleonitrile and 4-(N,N-diethylamino)salicylaldehyde. Compared with H2L at 293 K, a low temperature of 100 K makes the parallel aromatics in H2L come closer and fluorescence emission becomes weaker because of π-π interaction-caused quenching. After grinding the crystals of H2L, the colour changed from dark brown-red to yellow under room light and the fluorescence emission enhanced about 9-fold due to the damage of the intermolecular hydrogen bonds, leading to a decrease of non-radiative transition. H2L showed aggregation-induced emission enhancement (AIEE) characteristics in THF/H2O, whose mechanism is attributed to the restriction of intramolecular rotation (RIR). The UV-Vis spectra of H2L with Cu2+ in THF/H2O showed that at first a CuL complex was formed and subsequently a CuL' complex (H2L' = N',N'-bis(4-N',N'-diethylsalicylidene) ethylenediamine) was obtained. The CuL complex turned into the CuL' complex as time prolonged. H2L acted as a dual channel chemosensor for Cu2+ ions in THF/HEPES (v/v: 2 : 8, pH = 8.0) and the CuL complex was stable in this medium. H2L is also a naked-eye probe for Mn2+ ions in CH3CN. The limits of detection are much lower than the allowable level of copper(ii) and manganese(ii) in drinking water set by the World Health Organization (WHO).

5.
Inorg Chem ; 56(2): 984-990, 2017 Jan 17.
Article in English | MEDLINE | ID: mdl-28054772

ABSTRACT

2-(Trityliminomethyl)-quinolin-8-ol (HL) and its Zn(II) complex were synthesized and characterized by single-crystal X-ray diffraction. HL is an unsymmetrical molecule and coordinated with Zn(II) ion to form ZnL2 in the antiparallel-mode arrangement via Zn-O (hydroxyl group) and Zn-N (quinoline ring) of HL. A high degree of ZnL2 molecules ordering stacking is formed by the coordination bonds and intermolecular π-π interactions, in which head-to-tail arrangement (J-mode stacking) for L- is found. HL is nonfluorescent and ZnL2 is weakly fluorescent in THF. The fluorescence emission of ZnL2 enhances in THF/H2O as H2O% (volume %) is above 60% and aggregates particles with several hundred nanometers are formed, which is confirmed by DLS data and TEM images. The J-aggregates stacking for L- in ZnL2 results in aggregation-induced emission enhancement (AIEE) for ZnL2 in THF/H2O. Theoretical computations based on B3LYP/6-31G(d, p) and TD-B3LYP/6-31G(d, p) methods were carried out. ESIPT is the supposed mechanism for fluorescent silence of HL, and fluorescence emission of ZnL2 is attributed to the restriction of ESIPT process. The oscillator strength of ZnL2 increases from 0.017 for monomer to 0.032 for trimer. It indicates that a high degree of ZnL2 molecules ordering stacking in THF/H2O is of benefit to fluorescence enhancement. HL is an ESIPT-coupled AIEE chemosensor for Zn(II) with high selectivity and sensitivity in aqueous medium. HL can efficiently detect intracellular Zn(II) ions because of ESIPT-coupled AIEE property of ZnL2 in mixed solvent.

6.
Dalton Trans ; 45(20): 8316-9, 2016 May 28.
Article in English | MEDLINE | ID: mdl-27126357

ABSTRACT

The compounds of 3-aminopyridine-2-carboxylic acid with K(+) (1) and Zn(2+) (2) were found to be AIE-active. The AIE behaviours could be attributed to the restriction of intramolecular rotation (RIR) and vibration (RIV) via hydrogen bonds, resulting in rigidity enhancement of the molecules. An AIE-based fluorescence turn on chemosensor for the Zn(ii) ion has been developed in aqueous media with high selectivity and sensitivity.

7.
J Colloid Interface Sci ; 471: 1-6, 2016 Jun 01.
Article in English | MEDLINE | ID: mdl-26967663

ABSTRACT

A microscale metal-organic framework [Eu(atpt)1.5(phen)(H2O)]n (H2atpt=2-aminoterephthalic acid, phen=1,10-phenanthroline) (Eu-MOF) was synthesized and characterized by elemental analysis, luminescence spectrum, powder X-ray diffraction, dynamic light scattering and scanning electron microscope. The fluorescence response of Eu-MOF to metal ions and aldehydes showed that Eu-MOF is highly selective to Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde (2-OH-NA). Eu-MOF could be utilized as a multi-functional fluorescence chemosensor for Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde (2-OH-NA). The detection limit of Fe(III), Al(III) and 2-OH-NA was 45, 10 and 36µM, respectively. The corresponding sensing mechanisms were explored.

8.
Dalton Trans ; 44(11): 5191-6, 2015 Mar 21.
Article in English | MEDLINE | ID: mdl-25686207

ABSTRACT

A quinazoline-based fluorescence chemosensor, 6-phenol-2-yl-(5,6-dihydrobenzimidazo[1,2-c])quinazoline (HL), for highly selective recognition of Cu(II) in aqueous media was synthesized. The detection limit was of the order of 10(-6) M. The crystal structures of the Cu(II) and Cd(II) complexes showed that HL changed to a Schiff base when it reacts with metal salts and that the metal ions coordinate with two nitrogen atoms and one hydroxyl oxygen atom from the Schiff base. The theoretical calculations at B3LYP-SCRF/6-31G(d) confirmed that it is the Cu(II) ion that assisted the ring-opening of the quinazoline derivative, forming a Cu(II) Schiff base complex during the detection. LMCT leads to the disappearance of fluorescence. A cell imaging study indicated that HL could be used to detect the intracellular Cu(2+) ion.


Subject(s)
Benzimidazoles/chemistry , Cadmium/chemistry , Chemistry Techniques, Analytical/instrumentation , Copper/analysis , Quinazolines/chemistry , Water/chemistry , HeLa Cells , Humans , Intracellular Space/chemistry , Models, Molecular , Molecular Conformation , Molecular Imaging
9.
Inorg Chem ; 53(23): 12234-6, 2014 Dec 01.
Article in English | MEDLINE | ID: mdl-25393950

ABSTRACT

Two new heterometallic coordination polymers, [Na4Ln12(stp)8(OH)16(H2O)12]·10H2O [Ln = Dy (1) and Ho (2)], have been prepared from monosodium 2-sulfoterephthalate (NaH2stp), dysprosium acetate, or holmium acetate. They are isostructural, possessing a [Ln12(µ3-OH)16](20+) wheel-cluster core based on four vertex-sharing cubane-like [Ln4(µ3-OH)4](8+) units. The Ln12 cores are linked by stp ligands into a three-dimensional (3D) architecture. Magnetic studies indicate that complex 1 exhibits slow relaxation of magnetization, and it can be regarded as the first 3D coordination assembly of a Dy12 cluster single-molecule magnet.

10.
Dalton Trans ; 43(19): 7298-303, 2014 May 21.
Article in English | MEDLINE | ID: mdl-24691498

ABSTRACT

Two new Schiff base complexes, [ZnL(Ac)]2 (1) and [CuLCl]·H2O (2) (HL = 2-(2'-hydroxynaphthylmethylene)aminophenylbenzimidazole, Ac = acetate) were synthesized by a one-pot reaction and characterized by elemental analyses, IR and single-crystal X-ray diffraction. Fluorescence of complex 1 showed "on-off-on" switching when Cu(2+) and cyanide were sequentially detected. This phenomenon was investigated by UV-Vis absorption, fluorescence and ESI-MS spectra, and theoretical calculations to explain the response. Complex 1 can selectively respond to Cu(2+) with the fluorescence "turn-off" owing to the formation of complex 2 in the solution. Interestingly, the quenched fluorescence of complex 1 by Cu(2+) ions could be turned on after the addition of cyanide owing to the displacement of L(-) by CN(-) to form [Cu(CN)x](n-), making complex 1 a selective CN(-) probe. In addition, the results of the MTT assay experiment indicate that complex 1 has a low toxicity to cells and can be used to detect intracellular Cu(2+) ion by live cell imaging.


Subject(s)
Coordination Complexes/chemistry , Copper/analysis , Cyanides/analysis , Spectrophotometry, Ultraviolet , Zinc/chemistry , Cell Survival/drug effects , Coordination Complexes/chemical synthesis , Coordination Complexes/toxicity , Crystallography, X-Ray , HeLa Cells , Humans , Microscopy, Confocal , Molecular Conformation , Quantum Theory , Schiff Bases/chemistry , Spectrometry, Mass, Electrospray Ionization
11.
Dalton Trans ; 43(17): 6429-35, 2014 May 07.
Article in English | MEDLINE | ID: mdl-24615141

ABSTRACT

A tetrazole derivative 1-[(1H-tetrazol-5-ylimino)methyl]naphthalen-2-ol (H2L) as a fluorescent chemosensor for Al(3+) in DMSO and Zn(2+) in DMF was designed and synthesized. From (1)H NMR data, the Job plot and the ESI-MS spectrum, 1 : 1 stoichiometric complexation between H2L and Al(3+)/Zn(2+) was found in DMSO and DMF, respectively. The theoretical calculations at the level of B3LYP/6-311G** for the ground state and TD-B3LYP/6-311G** for the excited state revealed the sensing mechanism is the inhibition of excited state intramolecular proton transfer (ESIPT). And the possible fluorescent species formed in the DMSO and DMF solutions were deduced to be [Al(HL)(OH)(NO3)(H2O)(DMSO)] and [Zn(HL)(OH)(H2O)(DMF)]. What's more, it is confirmed that H2L could be used to detect Al(3+) and Zn(2+) in cells by bioimaging.


Subject(s)
Aluminum/analysis , Fluorescent Dyes/chemistry , Microscopy, Confocal , Tetrazoles/chemistry , Zinc/analysis , Fluorescent Dyes/metabolism , HeLa Cells , Humans , Ions/chemistry , Solvents/chemistry
12.
Inorg Chem ; 53(6): 3012-21, 2014 Mar 17.
Article in English | MEDLINE | ID: mdl-24571390

ABSTRACT

This paper reports a fluorescence chemosensor, N-(benzimidazol-2-yl)salicylaldimine (H2L), for Zn(II) and Al(III) ions. H2L has high selectivity for Al(III) in dimethyl sulfoxide (DMSO) and for Zn(II) in N,N-dimethylformamide (DMF). In methanol, Zn(II) and Al(III) could also be distinguished by H2L with different excitation wavelengths. The fluorescent species [Zn(HL)(H2O)(CH3OH)](+), [Zn(HL)(H2O)(DMF)](+), [Al(HL)2(OH)(H2O)], and [Al(HL)(OH)2(H2O)(DMSO)] formed in solution were established by a combination of experimental and theoretical methods, including Job's plot, (1)H NMR titration, electrospray inonization mass spectrometry (ESI-MS), and B3LYP-SCRF/6-31(d) and TD-B3LYP-SCRF/6-31G* density functional theory methods. The results show that Zn(II) and Al(III) are all coordinated to the imine nitrogen atom and the hydroxyl oxygen atom from H2L, which is the same as the M(2+) ions in the obtained mononuclear complexes [M(HL)2(CH3OH)2] (where M = Cd, Ni, Co, and Mg). The detection limits of H2L for Zn(II) were 5.98 µM in methanol and 5.76 µM in DMF, while the detection limits of H2L for Al(III) were 3.3 µM in methanol and 5.25 µM in DMSO. Furthermore, it is also confirmed that H2L has low toxicity for HeLa cells and could be used to detect Zn(II) and Al(III) ions in living cells by bioimaging.


Subject(s)
Aluminum/chemistry , Zinc/chemistry , Crystallography, X-Ray , Proton Magnetic Resonance Spectroscopy , Spectrometry, Mass, Electrospray Ionization
13.
Inorg Chem ; 52(13): 7320-2, 2013 Jul 01.
Article in English | MEDLINE | ID: mdl-23786342

ABSTRACT

A chemosensor for the Al(3+) ion, 1-[(3-hydroxypyridin-2-ylamino)methylene]naphthalen-2(1H)-one (H2L), based on inhibited excited-state intramolecular proton transfer was synthesized. The experimental and theoretical calculations at B3LYP+PCM/6-31G(d) revealed that Al(3+) and H2L form a 1:1 complex, [AlL(OH)(H2O)]2, in dimethyl sulfoxide that exhibits two remarkably enhanced fluorescent emissions at 523 and 553 nm. It is confirmed that H2L could be used to detect Al(3+) ions in cells by bioimaging.


Subject(s)
Aluminum/analysis , Fluorescent Dyes/chemistry , Cations/analysis , HeLa Cells , Humans , Models, Molecular , Naphthalenes/chemistry , Optical Imaging , Spectrometry, Fluorescence
14.
Chem Asian J ; 8(1): 95-100, 2013 Jan.
Article in English | MEDLINE | ID: mdl-23081854

ABSTRACT

Four new three-dimensional isostructural lanthanide-cadmium metal-organic frameworks (Ln-Cd MOFs), [LnCd(2)(imdc)(2)(Ac)(H(2)O)(2) ]·H(2)O (Ln=Pr (1), Eu (2), Gd (3), and Tb (4); H(3)imdc=4,5-imidazoledicarboxylic acid; Ac=acetate), have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, inductively coupled plasma (ICP) analysis, and X-ray diffraction. Single-crystal X-ray diffraction shows that two Ln(III) ions are surrounded by four Cd(II) ions to form a heteronuclear building block. The blocks are further linked to form 3D Ln-Cd MOFs by the bridging imdc(3-) ligand. Furthermore, the left- and right-handed helices array alternatively in the lattice. Eu-Cd and Tb-Cd MOFs can emit characteristic red light with the Eu(III) ion and green light with the Tb(III) ion, respectively, while both Gd-Cd and Pr-Cd MOFs generate blue emission when they are excited. Different concentrations of Eu(3+) and Tb(3+) ions were co-doped into Gd-Cd/Pr-Cd MOFs, and tunable luminescence from yellow to white was achieved. White-light emission was obtained successfully by adjusting the excitation wavelength or the co-doping ratio of the co-doped Gd-Cd and Pr-Cd MOFs. These results show that the relative emission intensity of white light for Gd-Cd:Eu(3+),Tb(3+) MOFs is stronger than that of Pr-Cd:Eu(3+),Tb(3+) MOFs, which implies that the Gd complex is a better matrix than the Pr complex to obtain white-light emission materials.

15.
Inorg Chem ; 51(3): 1201-3, 2012 Feb 06.
Article in English | MEDLINE | ID: mdl-22273471

ABSTRACT

Five novel 3D heterometallic lanthanide-zinc-organic frameworks, [H(H(2)O)(8)][LnZn(4)(imdc)(4)(Him)(4)] [Ln = La (1), Pr (2), Eu (3), Gd (4), Tb (5); H(3)imdc = 4,5-imidazoledicarboxylic acid; Him = imidazole], were synthesized via an in situ hydrothermal reaction, and tunable luminescence from yellow to white was obtained through the doping of Eu and Tb ions in the La-Zn framework.

16.
Dalton Trans ; 41(9): 2639-47, 2012 Mar 07.
Article in English | MEDLINE | ID: mdl-22222995

ABSTRACT

Hydro- and solvo-thermal reactions of d-block metal ions (Mn(2+), Co(2+), Zn(2+) and Cd(2+)) with monosodium 2-sulfoterephthalate (NaH(2)stp) form six 3D coordination polymers featuring cluster core [M(4)(µ(3)-OH)(2)](6+) in common: [M(2)(µ(3)-OH)(stp)(H(2)O)] (M = Co (1), Mn (2) and Zn (3)), [Zn(2)(µ(3)-OH)(stp)(H(2)O)(2)] (4), [Zn(4)(µ(3)-OH)(2)(stp)(2)(bpy)(2)(H(2)O)]·3.5H(2)O (5) and [Cd(2)(µ(3)-OH)(stp) (bpp)(2)]·H(2)O (6) (stp = 2-sulfoterephthalate, bpy = 4,4'-bipyridine and bpp = 1,3-di(4-pyridyl)propane). All these coordination polymers were characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric and elemental analysis. Complexes 1-3 are isostructural coordination polymers with 3D frameworks based on the chair-like [Zn(4)(µ(3)-OH)(2)](6+) core and the quintuple helixes. In complex 4, there exist double helixes in the 3D framework based on the chair-like cluster cores. Complex 5 possesses a 2-fold interpenetration structure constructed from boat-like cluster core and the bridging ligands stp and bpy. For complex 6, the chair-like cluster cores and stp ligands form a 2D (4,4) network which is further pillared by bpp linkers to a 3D architecture. Magnetic studies indicate that complex 1 exhibits magnetic ordering below 4.9 K with spin canting, and complex 2 shows weak antiferromagnetic coupling between the Mn(II) ions with g = 2.02, J(wb) = -2.88 cm(-1), J(bb) = -0.37 cm(-1). The fluorescence studies show that the emissions of complexes 3-6 are attributed to the ligand π-π* transition.


Subject(s)
Metals, Heavy/chemistry , Phthalic Acids/chemistry , Crystallization , Fluorescence , Magnetics , Molecular Structure , Phthalic Acids/chemical synthesis , Thermogravimetry , X-Ray Diffraction
17.
Dalton Trans ; 40(8): 1758-67, 2011 Feb 28.
Article in English | MEDLINE | ID: mdl-21246144

ABSTRACT

Self-assembly of copper(ii) ion, 3,4-pyridinedicarboxylate (PDC), and 1,10-phenanthroline (phen) under basic conditions at 100 °C affords four PDC linked copper(ii) complexes, [Cu(4)(µ(2)-OH)(3)(µ(3)-OH)(PDC)(phen)(4)](n)·n(PDC)·11.5 nH2O (1), [Cu(4)(µ(2)-OH)(2)(µ(3)-OH)(2)(PDC)(phen)(4)](n)·n(PDC)· 11.5 nH(2)O (2), [Cu(8)(µ(2)-OH)(2)(µ(3)-OH)(6)(PDC)(2)(phen)(8)]·2(PDC)·23 H(2)O (3), and [Cu(3.5)(µ(2)-OH)(3) (PDC)(2)(phen)](n) (4). 1-4 are copper hydroxo complexes, and 1, 2 and 3 co-crystallized from the one-pot reaction. X-ray single crystal diffraction analyses indicate that complexes 1 and 2 are linkage isomers and contain tetranuclear copper cluster cores with different geometry, and that PDC links the cluster core to form a one-dimensional chain. Complex 3 is a discrete step-like octanuclear copper hydroxo cluster complex. The involvement of hydroxo and phen in the coordination makes some coordination sites of PDC idle, which leads to rich hydrogen bonds and π-π interactions in complexes 1, 2 and 3. Complex 4 contains two types of copper hydroxo cluster cores: chair-like tetranuclear and linear trinuclear units, and the cluster cores are linked by PDC to a double-layer metal-organic framework. Magnetic properties of 1, 3 and 4 were investigated. The results reveal that complexes 3 and 4 exhibit strong antiferromagnetic interactions whereas ferromagnetic coupling is predominant for complex 1. The magnetic properties are analyzed in connection with their structures.


Subject(s)
Copper/chemistry , Organometallic Compounds/chemistry , Picolinic Acids/chemistry , Crystallography, X-Ray , Magnetics , Models, Molecular , Phenanthrolines/chemistry , Temperature
18.
Inorg Chem ; 47(12): 5225-33, 2008 Jun 16.
Article in English | MEDLINE | ID: mdl-18489090

ABSTRACT

Four copper(II) complexes [Cu3(PZHD)2(2,2'-bpy)2(H2O)2].3H2O (1), [Cu3(DHPZA)2(2,2'-bpy)2] (2), [Cu(C2O4)phen(H2O)].H2O (3), and [Cu3(PZTC)2(2,2'-bpy)2].2H2O (4) were synthesized by hydrothermal reactions, in which the complexes 1-3 were obtained by the in situ Cu(II)/H3PZTC reactions (PZHD3- = 2-hydroxypyrazine-3,5-dicarboxylate, 2,2'-bpy = 2,2'-bipyridine, DHPZA3- = 2,3-dihydroxypyrazine-5-carboxylate, C2O42- = oxalate, phen = 1,10-phenanthroline, and H3PZTC = pyrazine-2,3,5-tricarboxylic acid). The Cu(II)/H3PZTC hydrothermal reaction with 2,2'-bpy, without addition of NaOH, results in the formation of complex 4. The complexes 1-4 and transformations from H3PZTC to PZHD3-, DHPZA3-, and C2O4(2-) were characterized by single-crystal X-ray diffraction and theoretical calculations. In the complexes 1, 2, and 4, the ligands PZHD3-, DPHZA3-, and PZTC3- all show pentadentate coordination to Cu(II) ion forming three different trinuclear units. The trinuclear units in 1 are assembled by hydrogen-bonding and pi-pi stacking to form a 3D supramolecular network. The trinuclear units in 2 acting as building blocks are connected by the carboxylate oxygen atoms forming a 2D metal-organic framework (MOF) with (4,4) topology. While the trinuclear units in 4 are linked together by the carboxylate oxygen atoms to form a novel 2D MOF containing right- and left-handed helical chains. The theoretical characterization testifies that electron transfer between OH- and Cu2+ and redox of Cu 2+ and Cu+ are the most important processes involved in the in situ copper Cu(II)/H3PZTC reactions, forming complexes of 1-3.

19.
Article in English | MEDLINE | ID: mdl-17954035

ABSTRACT

Fluorescence of terbium(III) is sensitized when excited in the presence of ciprofloxacin (CPLX) in the aqueous solution because a Tb(III)-CPLX complex is formed and the maximum fluorescence peak locates at 545 nm. The second-order scattering (SOS) peak at 545 nm also appears for the Tb(III)-CPLX complexes with the excitation wavelength of 272 nm. The intensity at 545 nm obviously increases when the silver nanoparticles are added to the Tb(III)-CPLX system, and the relative intensity is proportional to the concentration of CPLX. Based on this phenomenon, a new method for the determination of CPLX has been developed by using a common spectrofluorometer to measure the intensity of fluorescence and SOS. The intensity is enhanced most by silver nanoparticles at pH 6.0. The calibration graph for CPLX is linear in the range of 3.0 x 10(-9) to 1.0 x 10(-5) mol l(-1). The detection limit is 8.5 x 10(-10) mol l(-1). The method was applied satisfactorily to the determination of CPLX in tablets and capsules. The results show that silver nanoparticles with certain size and concentration can enhance the fluorescence and SOS intensity of the system.


Subject(s)
Ciprofloxacin/chemistry , Nanoparticles/chemistry , Scattering, Radiation , Silver/chemistry , Terbium/chemistry , Buffers , Calibration , Capsules , Ciprofloxacin/analysis , Hydrogen-Ion Concentration , Nanoparticles/ultrastructure , Particle Size , Solutions , Spectrometry, Fluorescence , Tablets
20.
Inorg Chem ; 46(8): 2956-8, 2007 Apr 16.
Article in English | MEDLINE | ID: mdl-17355129

ABSTRACT

Three novel coordination polymers, [LnCu(PZDC)3].[Ln(H2O)9]0.5.[(H2O)7H+]0.5 [Ln = La (1), Eu (2), Gd (3)], were synthesized. They are the first 3d-4f heterometallic framework with supramolecular 1D channels, in which lanthanide hydrate cations and lattice water molecules are located.


Subject(s)
Copper/chemistry , Lanthanoid Series Elements/chemistry , Organometallic Compounds/chemical synthesis , Crystallography, X-Ray , Models, Molecular , Molecular Structure , Organometallic Compounds/chemistry
SELECTION OF CITATIONS
SEARCH DETAIL
...