脱羧
In situ hydrothermal syntheses,structures and photoluminescent
properties of four novel metal-organic frameworks constructed by
lanthanide(Ln?Ce(III),Pr(III),Eu(III))and Cu(I)metals with?exible dicarboxylate acids and piperazine-based ligands
Burak Ay a,Serkan Karaca a,Emel Yildiz a,n,Valerie Lopez b,Max H.Nanao d,e,Jon Zubieta b,c
a Department of Chemistry,Arts and Science Faculty,?ukurova University,01330Adana,Turkey
b Department of Chemistry,Syracuse University,Syracuse,NY13244,USA
c UniversitéGrenoble Alpes Laboratoire de Physiologie Cellulaire&Végétale,Institut de Recherches en Technologies et Sciences pour le Vivant,17rue des
Martyrs,38054Grenoble cedex9,France
d European Molecular Biology Laboratory,Grenobl
e Outstation,71Avenue des Martyrs,CS90181,38042Grenoble Cedex9,France
e University Grenoble Alpes-Centre National de la Recherche Scienti?que-EMBL Unit o
f Virus Host-Cell Interactions,71Avenue des Martyrs,CS90181,38042
Grenoble Cedex9,France
a r t i c l e i n f o
Article history:
Received27August2015
Received in revised form
16October2015
Accepted21October2015
Available online3November2015
Keywords:
Hydrothermal synthesis
Piperazine
Copper(I)polymer
Luminescence
Multiple decarboxylation
Cuprophilic interaction
a b s t r a c t
Four novel metal-organic frameworks,[Cu2Cl2(pyrz)]n(1)and(H2pip)n[Ln2(pydc)4(H2O)2]n(Ln?Ce(2),Pr
(3)and Eu(4),H2pzdc?2,3-pyrazinedicarboxylic acid,pyrz?pyrazine,H2pydc?2,6-pyridinedicarboxylic
acid,H2pip?piperazine)have been synthesized under hydrothermal conditions and characterized by the
elemental analysis,ICP,Far IR(FIR),FT-IR spectra,TGA,single crystal X-ray diffraction analysis and
powder X-ray diffraction(PXRD).Compound1is two-dimensional containing Cl-Cu-Cl sites,while the
lanthanide complexes contain one-dimensional in?nite Ln–O-Ln chains.All the complexes show high
thermal stability.The complexes1–3exhibit luminescence emission bands at584,598and614nm at
room temperature when excited https://www.sodocs.net/doc/d78431662.html,plex4exhibits bright red solid-state phosphorescence
upon exposure to UV radiation at room temperature.
&2015Elsevier Inc.All rights reserved.
1.Introduction
The design and synthesis of metal-organic frameworks(MOFs),
also referred to as porous coordination polymers(CPs),is one of
the most important research areas in crystal engineering[1].MOFs
exhibiting interesting structures and topologies are of great in-
terest not only for their unique structural and functional proper-
ties,but also for their potential applications in a variety of areas,
including catalysis,luminescence,gas storage,sensors,ion con-
ductivity,and magnetic materials[2–5].Surfactant-thermal and
solvo-hydrothermal methods have been used in the preparation of
MOFs[6,7].Judicious ligand selection is a major consideration for
the synthesis of MOFs.Multidentate N and O-donor bridging
pyridine or pyrazine carboxylic acid ligands have been extensively
used for the construction of novel systems.Among these ligands,
H2pzdc and H2pydc are suitable for preparing multifunctional CPs
for several reasons:(a)they can be partially or completely de-
protonated to provide didderent charge states by controlling the
pH values;(b)the carboxylic groups possess high symmetry and
considerable structural?exibility;(c)the ligand may coordinate to
metal atoms via the carboxyl and nitrogen atoms in a variety of
modes.A variety of coordination types of pzdc2àand pydc2àhave
been reported previously[8–12].The structures constructed using
the H2pzdc ligands in a variety of coordination modes and the D-
block transition metals are generally one-and two-dimensional
[13–15],while those of lanthanides with H2pzdc ligands are al-
most exclusively three-dimensional architectures[16–18].
The hydrothermal method provides an ef?cient technique for
synthesizing MOFs.Factors such as variations in temperature,pH,
reactant stoichiometry,the presence or absence of organic cations,
and even the?ll volume have been shown to in?uence the product
outcome[19,20].Furthermore,while multidentate carboxylic acid
ligands can easily decarboxylate under hydrothermal conditions
[21,22],decarboxylation reactions of multiple carboxyl groups are
rarely encountered.Chen et al.’s reported on the in situ
Contents lists available at ScienceDirect
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Journal of Solid State Chemistry
https://www.sodocs.net/doc/d78431662.html,/10.1016/j.jssc.2015.10.033
0022-4596/&2015Elsevier Inc.All rights
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n Correspoding author.Fax:903223386070.
E-mail address:eeyildiz@https://www.sodocs.net/doc/d78431662.html,.tr(E.Yildiz).
Journal of Solid State Chemistry233(2016)415–421
decarboxylation that resulted in H 2pzdc ’s losing both carboxyl groups through catalysis by Keggin polyoxometalates to produce pyrazine bridged 1D and 2D polyoxometalates [23].We observed multiple decarboxylation during the synthesis of the complex 1in the absence of catalyst under hydrothermal conditions as reported in this work.As shown in Scheme 1decarboxylation resulted in pyrazine acting as a bidentate ligand.
In a related study,Natarajan et al.’s reported a 1D Bi 3tco-ordination polymer incorporating this heterocyclic aromatic car-boxylic acid ligand [24].In this study,we report three new one-dimensional CPs incorporating Ce 3t,Pr 3tand Eu 3tof a similar composition but under different hydrothermal reaction conditions.
The aim of the present work is the synthesis and character-ization of novel MOFs containing H 2pydc,H 2pip,or H 2pzdc acid and its decarboxylation product pyrazine.We report a two-di-mensional Cu(I)and three one-dimensional Ln(III)(Ln ?Ce,Pr and Eu)CPs constructed from ?exible organic ligands and compare their luminescent properties.The lanthanide CPs are isomorphous,exhibiting interesting 1D frameworks.In contrast,unexpected multiple decarboxylation occurred during the synthesis of 1and produced pyrazine ligand as a bidentate ligand.To our knowledge,the copper(I)complex represents the ?rst example of a multiple decarboxylation reaction under hydrothermal conditions in the absence of a catalyst.
2.Experimental
2.1.Materials and methods
All chemicals and solvents were obtained from commercial sources and used without further puri ?cation.Distilled water was used all synthesis and catalytic reactions.The pH of the solutions were measured prior to and after heating using a Hanna pH meter.All hydrothermal syntheses were carried out in 23mL PTFE-lined stainless steel containers under autogenous pressure.IR spectra were measured with Thermo Scienti ?c Nicolet IS10Model FT-IR Spectrophotometer using ATR method with a resolution of 4cm à1at room temperature.Far infrared analysis was performed with a Perkin Elmer Spotlight 400model Spectrophotometer in the re-gion 700–30cm à1.Thermo Flash 2000CHNS Elemental Analyzer was used for elemental analysis.The inductively coupled plasma (ICP)analysis was carried out on a Perkin –Elmer Optima 2100DV ICP instrument.TGA analyses were conducted in nitrogen atmo-sphere with Perkin Elmer Pyris Diamond TG/DTA equipment at a heating rate of 10°C min à1.Rigaku Mini ?ex system with CuK αradiation (λ?1.54059?)was used for the PXRD studies.Solid state ?uorescence excitation and emission spectra were recorded on a Perkin –Elmer LS 55Luminescence Spectrometer.2.2.Synthesis of [Cu 2Cl 2(pyrz)]n
A solution of copper(II)chloride dihydrate (0.103g,0.60mmol),2,3-pyrazinedicarboxylic acid (0.101g,0.60mmol),oxalic acid
(0.03g,0.33mmol)and H 2O (10mL,556mmol)with the mole ratio of 1.82:1.82:1:1685was stirred brie ?y before heating 180°C for 120h.The initial and ?nal pH values were 2.00and 5.00,re-spectively.The heterogeneous solution mixture was separated from the solid phase and the crystals washed with water and dried at room temperature.Orange crystals suitable for X-ray diffraction were isolated in 81%yield.The coordination polymer is insoluble in common solvents (ethanol,methanol,acetonitrile,etc.)Anal.Calcd.for C 2H 2NClCu:C,17.26;H,1.44;N,10.07.Found:C,17.88;H,1.65;N,9.97%.The ICP analysis (%)showed that 1contained Cu:44.02;Calcd.:Cu:45.68.IR data (cm à1):1474(m),1411(s),1353(w),1157(m),1113(m),1055(m),800(s),447(s),150(m),122(m).2.3.Synthesis of (H 2pip)n [Ce 2(pydc)4(H 2O)2]n
A solution of cerium (III)nitrate hexahydrate (0.130g,0.30mmol),2,6-pyridinedicarboxylic acid (0.150g,0.90mmol),piperazine (0.078g,0.90mmol),and H 2O (5mL,278mmol)with the mole ratio of 1:3:3:927was stirred before heating at 170°C for 60h.The initial and ?nal pH values were 6.00and 6.55,rspec-tively.The heterogeneous solution mixture was separated from the solid phase and the crystals washed with water and dried at room temperature.Bright yellow crystals suitable for X-ray diffraction were isolated in 81.4%yield (based on Ce).Anal.Calcd.for C 16H 13N 3O 9Ce:C,36.13;H,2.45;N,7.90.Found:C,36.51;H,2.84;N,7.83%.The ICP analysis (%)showed that 2contained Ce:25.62;Calcd.:Ce:26.37.IR data (cm -1):3358(m),3034(m),2812(w),1608(s),1566(s),1431(s),1368(s),1275(m),1071(m),725(s),661(s),580(m),517(m),411(m).
2.4.Synthesis of (H 2pip)n [Pr 2(pydc)4(H 2O)2]n
The preparation of 3was similar to that of 2except that Pr(NO 3)3á6H 2O (0.130g,0.30mmol)was used instead of Ce(NO 3)3á6H 2O.Green crystals suitable for X-ray diffraction were isolated in 73.3%yield (based on Pr).Anal.Calcd.for C 16H 13N 3O 9Pr:C,36.08;H,2.44;N,7.89.Found:C,36.56;H,2.87;N,7.90%.The ICP analysis (%)showed that 3contained Pr:25.50;Calcd.:Pr:26.48.IR data (cm -1):3360(m),3035(m),2814(w),1579(s),1566(s),1439(s),1369(s),1266(m),1072(m),724(s),662(s),594(m),521(m),414(m).2.5.Synthesis of (H 2pip)n [Eu 2(pydc)4(H 2O)2]n
The preparation of 4was similar to that of 2except that Eu(NO 3)3.5H 2O (0.128g,0.30mmol)was used instead of Ce(NO 3)3á6H 2O.Colorless crystals suitable for X-ray diffraction were iso-lated in 77%yield (based on Eu).Anal.Calcd.for C 16H 13N 3O 9Eu:C,35.34;H,2.39;N,7.73.Found:C,35.48;H,2.44;N,7.78%.The ICP analysis (%)showed that 4contained Eu:26.80;Calcd.:Eu:27.97.IR data (cm à1):3382(m),3034(m),2832(w),1609(s),1569(s),1431(s),1370(s),1278(m),1074(m),730(s),694(m),662(m),575(m),414(m).
2.6.X-ray crystallography
Crystallographic data for compound 1were collected at low temperature (90K)on a Bruker KAPPA APEX DUO diffractometer equipped with an APEX II CCD system using Mo K αradiation (λ?0.71073?)[25].The data were corrected for Lorentz and po-larization effects [26],and adsorption corrections were made using SADABS [27].For compounds 2–4data were collected on the ESRF microfocus MX beamline ID23-EH2[28].A crystal was ?ash frozen in a gaseous Nitrogen stream at 100K,and oscillation data were collected on a Pilatus 3-2M detector (Dectris,Switzerland).The detector was set to the minimum possible distance,which is limited by the diffractometer and sample changer robotics
to
Scheme 1.Multiple decarboxylation reaction of H 2pzdc and its coordination mode in 1.
B.Ay et al./Journal of Solid State Chemistry 233(2016)415–421
416
1.06A at the edge.Higher resolution data can however be col-
lected at the corners of the detectors.No2theta movement exits
on this beamline,and the energy is?xed.14800.15°oscillations
were collected,with0.04s exposures,and99%attenuation of the
beam.Data were reduced with XDS[29].The data for the lan-
thanide materials2–4were collected on the Grenoble Synchrotron
Beam line using crystals of approximate0.02?0.01?0.005mm
dimensions.A narrow beam focus of dimensions10(H)?6
(V)microns was used for data collection.The wavelength was 0.8726?(14.209keV).
The structures were solved by direct methods,and structure
re?nement was carried out using the SHELXTL crystallographic
software[30].After assigning all non-hydrogen atoms,the models
were re?ned against F2?rst using isotropic and then using ani-sotropic thermal displacement parameters displacement para-
meters until the?nal value ofΔ/s max was less than0.001.The hydrogen atoms were introduced in calculated positions and then
re?ned isotropically.Neutral atom scattering coef?cients along
with anomalous dispersion corrections were taken from the In-
ternational Tables,Vol.C.Crystallographic details for the struc-
tures of1–4are summarized in Table1.Atomic positional para-
meters and isotropic temperature factors are given in Table S1-4
for1–4,respectively.Selected bond lengths and angles for struc-
tures1–4are provided in Table S5.Images of the crystal structures
were generated using CrystalMaker[31].Full tables of crystal
parameters and experimental conditions,atomic positional para-
meters and isotropic displacement parameters,bond lengths and
angles,anisotropic temperature factors,hydrogen atom co-
ordinates,and torsion angles for1–4are available from the Cam-
bridge Crystallographic Data Centre(see Appendix A).
3.Results and discussion
3.1.X-ray structural studies
As shown in Fig.1,the structure of[Cu2Cl2(pyrz)]n(1)is two
dimensional with the layers aligned normal to the crystallographic
110direction;the layer stacking is displayed in Fig.2.The layer is
constructed from{CuCl}n chains linked through the bridging pyr-
azine ligands.Within the chain,each Cu(I)site bonds to three
adjacent chloride ligands that bridge the copper site to three
neighboring copper atoms.Each chloride ligand in turn bridges
three copper centers to provide a ruf?ed ladder aspect to the
chain;this is acommon motif in the crystal chemistry of copper-halide based coordination polymers[32].The distorted tetrahedral coordination at the copper sites is completed by a pyrazine ni-trogen donor to give overall{CuCl3N}coordination.
Copper(I)compounds often show short Cu–Cu contacts(cu-prophilicity).In compound1,copper centers exhibit Cu–Cu dis-tances of2.876(1)?.Although this value is slightly larger than the sum of van der Waals radii of two copper atoms(2.80?),it is comparable to those reported for other copper(I)complexes,for example,[Cu2(m2-SH)2(PPh3)3](2.897?)[33],[(tpyprz)3Cu10Br10] (2.563?)[34]and[Cu(Cys-H)Cl](2.679?)[35].Such complexes with short Cu–Cu distances are known to display luminescence properties.
The lanthanide structures(H2pip)n[Ln2(pydc)4(H2O)2]n(Ln?Ce (2),Pr(3)and Eu(4))posed dif?culties in data collection due to their crystal habits.The compounds exhibited severely intergrown crystal clusters or stacks of extremely thin sheets.Consequently, data collection on a conventional diffractometer proved fruitless. However,we were able to exploit a?ne focus synchrotron beam to collect suitable data sets.The narrow beam width of the line al-lowed us to focus on clean crystal surfaces exposed at the edges of the crystal aggregates,and the high?ux of the beamline provided suitable diffraction intensities.
The structures of the three lanthanide materials are iso-morphous.As shown in Fig.3,the structures consist of Ln pydc H O
2422n
2n
[()()]?anionic chains with{H2pip}2tcations occu-pying the interchain domains.The chains,shown in Fig.4,consist of binuclear[Ln2(pydc)4(H2O)2]2àbuilding units linked through O, O′-bridging carboxylate groups.The lanthanide sites are nine co-ordinate through bonding to the nitrogen and carboxylate groups of the four pydc ligands of the binuclear unit,a carboxylate donor from the pydc ligand of a neighboring binuclear building unit and two aqua ligands.Within the binuclear unit the pydc ligands bond exclusively to a single Ln site through the nitrogen donor and one carboxylate terminus while the second carboxylate group of two pydc ligands bridges the two Ln centers through O,O-bridging and the second carboxylate termini of the remaining two pydc ligands engage in O,O′-bridging to link the binuclear unit to the two ad-jacent SBUs(secondary building blocks)[36].
3.2.IR spectra
In the IR spectrum of compound1no characteristic peaks of the carboxyl groups were observed because of the multiple dec-arboxylation reaction(Fig.S1).The strong and medium bands between1055and1706cmà1can be assigned to characteristic peaks of the pyrazine molecules(Fig.S2)[23].The very strong band observed at447cmà1is attributable to the Cu–N stretching vibration[37].To observe the Cu–Cl vibrations of complex1,far infrared(FIR)analysis carried out.The FIR spectra of compound1 (Fig.S3)exhibits two bands at150and122cmà1assigned to Cl–Cu–Cl bending modes[38].The infrared spectrum of the ligand H2pydc shows stretching bands attributed toυ(O–H),υ(C?O),υ(C?N)andυ(C–H)at3068,1688,1573and1080cmà1,respec-tively(Fig.S4).The IR spectra of the three as-synthesized iso-morphous lanthanide polymers are similar(Figs.S5–7)and exhibit broad bands in the regions around3382and3034cmà1associated with the O–H stretching vibrations of coordinated water molecules in the structures[39,40].In the IR spectra of the H2pydc,the C?O stretching frequency appeared at1688cmà1.After coordination, this strong peak shifted to1608,1579and1609cmà1for2–4, respectively,indicating that the oxygen atoms of the carbonyl group were also coordinated to lanthanide ions[41].The absorp-tions associated with the Ln–N and Ln–O stretching vibrations of the complexes were observed between594-410cmà1.The med-ium intensity bands at517and411cmà1may be ascribed toυ(Ce–N)andυ(Ce–O)[42].Bands,exclusive to the complexes and having
Table1
Summary of crystal data and data collection parameters for the structures of1–4.
Compound1234
Formula C2H2ClNCu C16H13N3O9Ce C16H13N3O9Pr C16H13N3O9Eu
T(K)90(2)100(2)100(2)100(2)
Fw139.04531.42532.20543.25
Crystal system Triclinic Triclinic Triclinic Triclinic
Space group P-1P-1P-1P-1
a(?) 3.725(6) 6.990(1) 6.970(1) 6.975(1)
b(?) 6.847(10)10.890(2)10.900(2)10.940(3)
c(?)7.472(11)12.340(3)12.330(3)12.342(3)
α(°)106.514(3)112.70(3)112.70(3)112.70(3)
β(°)97.560(3)96.08(3)95.85(3)95.95(3)
γ(°)91.716(3)94.80(3)94.80(3)94.82(3)
V,?180.660(5)853.7(3)851.9(3)852.7(6)
Z2222
D calcd(g/cmà3) 2.556 2.067 2.075 2.118
μ(mmà1) 6.534 2.728 2.921 3.743
Λ(?)0.710730.87260.87260.8726
R10.01710.0370.07970.0779
wR2(all data)0.04790.17630.18610.1946
B.Ay et al./Journal of Solid State Chemistry233(2016)415–421417
medium intensities at 521and 433cm à1,can be assigned to the υ(Pr –N)and υ(Pr –O)stretching vibrations [43].The corresponding υ(Eu –N)and υ(Eu –O)stretching vibrations were observed be-tween 575-430cm à1[44,45].These bands indicate that both the oxygen and nitrogen atoms coordinate the metal ions.The spectral data for 1–4are in good agreement with the X-ray crystal
structures of these compounds.3.3.Thermogravimetric analyses
All the coordination polymers are stable in air and insoluble in common solvents such as ethanol,methanol,hexane,ethyl acet-ate,acetone,acetonitrile,DMF and DMSO,except for 2that is slightly soluble in DMSO.Thermogravimetric (TG)analyses were carried out to examine the thermal stabilities of the compounds 1–4(Figs.S8–11).These were performed in the temperature range of 50-800°C under N 2atmosphere at 1atm with a heating rate of 10°C min àhttps://www.sodocs.net/doc/d78431662.html,pound 1is thermally stable up to 240°C,while the lanthanide complexes are stable only to ～200°C.The TGA curve of 1shows a single weight loss step from 240to 400°C,corresponding to the complete decomposition of the complex.Since all the lanthanide coordination polymers are isomorphous and have equal numbers of coordinated water and uncoordinated H 2pip molecules,they exhibit a similar weight loss pro ?le in the thermograms.For the sake of brevity,the pro ?le of complex 2is described in detail as a representative example.The all lanthanide complexes are thermally stable to 200°C.As shown by the TGA curve of 2in Fig.S9,decomposition occurs in three steps.The ?rst and second stages between 200and 360°C were attributed to the loss of one coordinated water and uncoordinated H 2pip groups per formula unit,with a weight loss percentage of 18.95%(Calcd.19.59%).The third weight loss of 63.17%,which occurred between 400and 550°C,corresponds to the decomposition of H 2pydc ligands (Calcd.62.89%).The fact that H 2pydc ligands are lost at a higher temperature is consistent with coordination to the lanthanide atoms.The ?nal product was CeO 2,and the observed weight (17.80%)was in good agreement with the calculated value (17.52%).The presence of LnO 2oxides was con ?rmed by iodine tests (Fig.S12).
3.4.Phase and purities of the compounds
To determinate the phase purities of the bulk products,the compounds were studied by powder X-ray diffraction (PXRD)at room temperature.The experimental powder XRD patterns of the 1–4(Figs.S13–14)are in good agreement with the simulated ones on the basis of the single-crystal structures,indicating the high purity of the synthesized samples.Also,elemental and ICP ana-lyses were consistent with the theoretical values.The differences in re ?ection intensities between the simulated and
experimental
Fig.1.A ball and stick representation of the structure of [Cu 2Cl 2(pyrz)]n (1).Color.scheme:copper,dark blue;chlorine,green;nitrogen,light blue;carbon,white.(For interpretation of the references to color in this ?gure legend,the reader is referred to the web version of this
article.)
Fig. 2.Ball and stick model of layers stacked in the crystal structure of [Cu 2Cl 2(pyrz)]n (1).
B.Ay et al./Journal of Solid State Chemistry 233(2016)415–421
418
patterns were due to the variation in the preferred orientation of the powder sample during collection of the experimental PXRD data.
3.5.Luminescence properties
The solid state photoluminescent properties of pyrz,pzdc 2à,pydc 2à(Fig.S15),as well as complexes 1–4,were investigated at room temperature.To understand the nature of the emission,the photoluminescent properties of the ligands were investigated.The free pyrz,pzdc 2àand pydc 2àligands show emission with a maximum at ca.324,415and 376nm upon excitation at 258,288and 325nm,respectively.These emissions of the ligands may be assigned to intraligand π*-n and π*-πtransitions.The emission spectra of 1–4were recorded from 500to 700nm under an ex-citation wavelength of 300nm at room temperature,and the re-sults are shown in Figs.5and 6a.1exhibits one strong emission with a peak maximum at 584nm upon excitation at 300nm.This is similar to that of the copper(I)compounds [46,47].Compared to the free pyrz ligand,the maximum emission of 1shows a greater red-shift (about 260nm).The luminescence emission spectra of isomorphous 2(Ce)and 3(Pr)complexes exhibit close emission bands centered at 598and 614nm,respectively.The emission spectra of 2is 222nm red-shifted compared to the free pydc 2à.
Similarly,the luminescence emission bands have visible red shifts in complex 3(238nm red-shifted)compared to that of the free pydc 2àligand.The red-shifted emissions are likely related to
the
Fig.3.A view of the crystal packing in (H 2pip)n [Eu 2(pydc)4(H 2O)2]n ,viewed along the a -axis.Color scheme:europium,gold;oxygen,red;carbon and oxygen as for Fig.1.(For interpretation of the references to color in this ?gure legend,the reader is referred to the web version of this
article.).
Fig.4.A view of the one-dimensional structure of the anionic component Eu pydc H O 2422n 2n [()()]?
.
Fig.5.Solid-state emission spectra of 1–3(λex ?300nm)at room temperature.
B.Ay et al./Journal of Solid State Chemistry 233(2016)415–421419
intraligand luminescence emissions [48].Complex 4exhibits strong bright red light luminescence with a standard laboratory UV lamp (254nm),and shows the characteristic emission bands for f –f transitions of the Eu(III)ion in the spectroscopy (Fig.6b).
The strong emission at 624nm is attributed to 5D 0-7F 2tran-sitions.The other strong emission at 603nm corresponds to the 5
D 0-7F 1transition,and the medium emission at 648nm is as-cribed to 5D 0-7F 3transitions.The emission bands observed for 4are similar to those of Eu(III)complexes [49–52].The results in-dicate that these CPs may serve as excellent candidates for po-tential photoluminescence materials,since they are thermally stable and insoluble in many common solvents.
4.Conclusions
In summary,copper(I)and lanthanum(III)CPs based on ?exible organic ligands have been successfully synthesized under hydro-thermal conditions.It is interesting to note that multiple dec-arboxylation was observed in 1.The pyrz was produced during the in situ multiple decarboxylation reaction of pzdc 2àwithout cata-lyst and was incorporated as a bidentate ligand through the N-donor atoms.In 2–4,the Ln(III)metal centers have the same coordination numbers and the H 2pydc ligands are coordinated through both the carboxylate oxygen and nitrogen groups,acting as tridentate ligands.The H 2pip is uncoordinated and resides be-tween metal-ligand chains of the one-dimensional https://www.sodocs.net/doc/d78431662.html,plex 4exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.Moreover,the photoluminescence spectra show that the compounds are the potential luminescent materials with maximum emission between 580and 700nm.
Acknowledgments
The authors gratefully acknowledge ?nancial support from the Research Unit of ?ukurova University (Grant no.FEF2013D5).JZ thanks the UniversitéGrenoble Alpes and the Institut de Re-cherches en Technologies et Sciences pour le Vivant for sabbatical support.
Appendix A.Supplementary material
Supplementary data associated with this article can be found in
the online version at https://www.sodocs.net/doc/d78431662.html,/10.1016/j.jssc.2015.10.033.
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