synthesis of a one-dimensional coordination polymer of

Research ArticleSynthesis of a One-Dimensional Coordination Polymer ofNickel(II) Complex with a 120573-Oxodithioester Ligand

Ricardo Rosas-Reyes1 Yasmi Reyes-Ortega2 T Jesus Morales-Juarez3

Virginia Goacutemez-Vidales4 and Ivan Garciacutea-Orozco1

1Laboratorio de Investigacion y Desarrollo de Materiales Avanzados (LIDMA) Facultad de QuımicaUniversidad Autonoma del Estado de Mexico Carretera Toluca-Atlacomulco Km 145 Unidad San Cayetano Toluca MEX Mexico2Centro de Quımica ICUAP Benemerita Universidad Autonoma de Puebla CU 72570 Puebla PUE Mexico3Facultad de Quımica Universidad Autonoma del Estado deMexico Paseo Colon esq Paseo Tollocan sn 50120 TolucaMEXMexico4Instituto de Quımica Universidad Nacional Autonoma de Mexico Circuito Interior Ciudad Universitaria Coyoacan01450 Mexico City Mexico

Correspondence should be addressed to Ivan Garcıa-Orozco igarciaouaemexmx

Received 31 May 2017 Revised 11 September 2017 Accepted 14 September 2017 Published 30 October 2017

Academic Editor Henryk Kozlowski

Copyright copy 2017 Ricardo Rosas-Reyes et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Bis-[methyl-1-hydroxy-1-cyclopentene-2-dithiocarboxylate-OS]nickel(II) 1 was prepared starting from methyl 2-hydroxycyclo-pent-1-encarbodithioate ligand (CPDT) and Ni(II) and catena-[(1205832-44

1015840-Bipyril)-bis-(methyl-2-hydroxy-1-cyclopentene-2-dithiocarboxylate-OS)]nickel(ΙΙ) 2 was prepared in good yields from 1 plus 441015840-bipyridyl (bpy) by shish-kebab methodology Thestructure of 1 was confirmed by FTIR elemental analysis 1H NMR UVndashvis in chloroform solution and in solid XPS and PXRDCompound 2 was characterized by FTIR elemental analysis UVndashvis in chloroform solution and in solid XPS PXRD ESR andsolid state magnetization measurements The structure of the polymer was established mostly by PXRD ESR and magnetization

1 Introduction

Discrete metallosupramolecular assemblies have been pre-pared towards potential applications in catalysis gas-storageseparation sensingmagnetism optics and electrochemistryamong others [1ndash6] The design of well-defined structuresis based on the directional-bonding approach using rigidligands with highly directional coordinating groups andgeometrically constrained metals entities In this sense thewheel-and-axle approach is being applied to obtain 1Dpolymers [7] which are also described as shish-kebab coor-dination polymers [8 9] This type of linear supramoleculesis formed when an ambidentate ligand bridges metallopor-phyrins with hexacoordinated metals [10] Shish-Kebab ap-proach has three variables (macrocycle bridging groupand transition metal) wherein metalloporphyrins were com-monly used as macrocycle-metal moiety andNN1015840-bidentateligands perform as bridging group towards the control ofoptical magnetic and electrical properties [11]

Not only are metalloporphyrins used in shish-kebabcoordination polymers but square planar complexes withtwo vacancies have also been used to obtain 1D coordina-tion polymers [12ndash14] We are interested in nickel(II) com-plexes with OS-donor ligands and in the study of the struc-ture and chemical properties given by the S-donor atoms inthe nickel coordination sphere Dorange et al reported thesynthesis of the NiL2 diamagnetic complex (L = methyl 3-hydroxy-3-phenyl-2-propenedithioate) [15] and a paramag-netic [NiL2(Py)2] bis-pyridine derivative This work showsthe possible use of bis-chelated complexes in square planarstructure for the preparation of shish-kebab coordinationpolymer with a 441015840-bipyridyl bridge Herein we reportthe syntheses and structural characterization of two nick-el(II) complexes bis-[Methyl 1-hydroxy-1-cyclopentene-2-dit-hiocarboxylate-OS] nickel(II) 1 and catena-[(1205832-44

1015840-bipyri-dyl)-bis-(methyl 2-hydroxy-1-cyclopentene-2-dithiocarboxy-late-OS)nickel(ΙΙ)] 2 starting from methyl 2-hydroxycyclo-pent-1-encarbodithioate ligand [16] and its 1D coordination

HindawiJournal of ChemistryVolume 2017 Article ID 7623210 7 pageshttpsdoiorg10115520177623210

2 Journal of Chemistry

polymer bridged by bpy The structure of the latter wasevidenced by spectroscopy in solid state being unstable insolution

2 Experimental Section

21 Materials and Methods Cyclopentanone methyl iodidepotassium tert-butoxide 441015840-bipyridyl (Aldrich) carbondisulfide and nickel(ii) chloride (J T Baker) were usedwithout further purification Solvents were distilled beforeuse Melting points were determined in a Melt-temp II 1Hand 13CNMR spectra were recorded using a Bruker-Advance300MHz spectrometer using TMS as internal standard IRspectra were recorded on a Nicolet Avatar 360 in KBr andATR FT-IR Shimadzu IR Prestige-21 model with 4 cmminus1 ofresolution Electronic absorption spectra were obtained on aPerkin Elmer lambda 25 spectrophotometerThe XPS spectrawere acquired using a JEOL JPS-9200 equipped with a MgX-ray source (12536 eV) at 200W the area of analysis was1mm and the vacuum was in the order of 10minus8 Torr forall samples The spectra were analyzed using the SpecSurfsoftware included with the instrument all spectra werecharge-corrected using the carbon signal (C 1s) at 2845 eV asa referenceThe Shirley method was used for the backgroundsubtraction while in the curve fitting process the Gauss-Lorentz method was used Electron Paramagnetic Resonancespectra were recorded on JOEL JES-TE300 of 14 T spectrom-eter operated on X-band at FM 100KHz in cylindrical cavityon TE011 method The samples were handled as solid intoWilmad quartz tubes Magnetization measurements wereperformed with a Quantum Design MPMS SQUID magne-tometerMPMS-5 Field-cooling (FC) cycle was performed atmagnetic field intensity of 1000Oe in the range 2 up to 300KPowder X-ray diffraction data were acquired in a Bruker D8advance diffractometer equipped with a Linxeye detectorusing Ni-filtered Cu K120572 radiation Tube conditions were30 kV 30 mA 2120579 range 5ndash50∘ step size 002∘ step time 32 s

22 Synthesis of the Methyl 2-Hydroxycyclopent-1-encarbod-ithioate Ligand (CPDT) To potassium tert-butoxide (83 g74mmol) in 200mL of dry ethyl ether was added cyclopen-tanone (3mL 34mmol) under stirring at minus10∘C After 30minutes a solution of CS2 (22mL 36mmol) in the samesolvent (20mL) was added continuing the stirring for 15 hmore Methyl iodide (22mL 36mmol) was then added anda reddish suspension was obtainedThe solvent was removedunder vacuum the solid was dissolved in water and acidifiedwith HCl 2M extracted with CH2Cl2 dried by Na2SO4and concentrated A yellow crystalline solid was obtainedby silica-gel chromatography using hexane as eluent Yield315 g (53) mp 376∘C IR (KBr cmminus1) 3427 br 2924m2853m 1644w 1553 s 1523m 1447m 1423w 1330w 1242m1072w 1020w 984w 949w 789w IR (ATR cmminus1) 2953w2915 w 2851 w 1547 s 1443m 1418m 1237m 793m 1HRMN (300MHz CDCl3) 120575 189 (q 2H 119869 = 74 79HzCH2CH2CH2) 263 (s 3H SCH3) 267 (t 2H 119869 = 79HzCH2CH2C=) 280 (t 2H 119869 = 74Hz C(O)CH2CH2) 1427 (1199041H OH) 13C NMR (75MHz CDCl3) 120575 1679 (SCH3) 1839

HOO OS

SS S

SS

2

1CPDT

NiNaOHNiCＦ2

EtOH

Scheme 1 Synthesis of 1 from CPDT ligand

(CH2CH2C=) 3079 (CH2CH2CH2) 3507 (C(O)CH2CH2)11930 (Cvin) 17947 (CO) 21363 (CS2) UVndashVis (CHCl3)[120582max nm (120576 Mminus1 cmminus1)] 319 (17650) 354 (13450) 374(17160)

23 Synthesis of bis-[Methyl 1-Hydroxy-1-cyclopentene-2-di-thiocarboxylate-OS]nickel(II) 1 An aqueous NaOH solution(5mL 04M) was added to a warm ethanolic solutionof CPDT (034 g 195mmol) under stirring NiCl2sdot6H2O(024 g 099mmol) in 25mL of ethanol was then addedto the mixture producing an orange solid The precipitatewas filtered and washed with ethanol and hexane yielding034 g (87) mp d250∘C Calc for C14H18NiO2S4sdotH2O C3973 H 476 S 3030 Found C 3989 H 431 S 3016IR (KBr cmminus1) 2904w 1546 s 1406 s 1287m 972w 934w910m 846w 669w IR (ATR cmminus1) 2951 w 2908w 2863w1545 s 1441 s 1409 s 1288w 847m 1H RMN (300MHzCDCl3) 120575 186 (m 2H 119869 = 76 78Hz CH2CH2CH2) 246(t 2H 119869 = 78Hz CH2CH2C=) 259 (s 3H SCH3) 265 (t2H 119869 = 76Hz C(O)CH2CH2) UVndashVis (CHCl3) [120582max nm(120576 Mminus1 cmminus1)] 238 (28330) 245 (26260) 277 (25350) 313(31160) 334 (25950) 378 (5600) 439 (4190) UVndashVis-NIR(solid) [120582max nm] 405 513 705

24 Synthesis of catena-[(1205832-441015840-Bipyridyl)-bis-(methyl 2-Hy-droxy-1-cyclopentene-2-dithiocarboxylate-OS)nickel(II)] 2 Asolution of bpy (008 g 053mmol) in 10mL of CHCl3 wasadded to a 50mL of chloroform solution of 1 (0104 g025mmol) under stirring at room temperature for 1 h Theyellow solid was filtered washed with CHCl3 and driedunder vacuum Yield 0106 g (73) mp d270∘C Calc forC24H26N2NiO2S4sdot025 CHCl3 C 4999 H 458 S 2201 N481 Found C 4985 H 446 S 2153 N 471 IR (ATRcmminus1) 2874w 2954w 2911 w 2834w 1575m 1483 s 1419 s1375 s 1274m 801m 727m 625m UVndashVis-NIR (solid)[120582max nm] 441 614 876 928 1008

3 Results and Discussion

31 Synthesis and Characterization of 1 1 was obtainedaccording to similar methodology (Scheme 1) previouslyreported for the nickel complexes of the methyl 3-hydroxy-3(41015840-R-phenyl)-2-propenedithiocarboxylate ligands [15]Theproposed structure of 1 was built by its spectroscopic charac-teristics and single crystal analysis

In the IR spectrum of 1 the loss of the centered bandis observed at 3427 cmminus1 which was assigned to H-O enolgroup in the ligand The signals at 1405 and 909 cmminus1 wereassigned to 120575(C-O) These signals were low energy-shifted

Journal of Chemistry 3

Table 1 Deconvoluted UVndashvis signals (nm) of compounds 1 and 2

Assignation 1 2CHCl3 solution

120587lowast larr 119899 O 280 279120572 120573-unsat 315 314120587lowast larr 119899 CS 337 336S-Ni LMCT 384 378O-Ni LMCT 445 442

Solid120587lowast larr 119899 CS 350 351S-Ni LMCT 399 406O-Ni LMCT 449 459

501 499714

3T1g(P) larr3A2g(]1) 571

3T1g(F) larr3A2g(]2) 886

3T2g(F) larr3A2g(]3) 934 922

respecting to the ligand (1422 and 949 cmminus1 Δ] = minus17 andminus39 cmminus1 resp) probably due to the O-Ni 120590-donation Thestretching mode of thiocarbonyl group (C=S) is observedat 1286 cmminus1 in the spectrum of 1 and this signal is highenergy-shifted from ligand (1242 cmminus1 Δ] = 44 cmminus1) [17]This fact could be provoked to the back donation of electrondensity from nickel to ligand The ](C=C) at 1545 cmminus1 isshifted towards lower wavenumbers from those of the ligand(1552 cmminus1 Δ] = minus7 cmminus1) The changes on C-O C=S andC=C energy vibrations suggest the electron delocalization onthe 6-membered chelated ring of the complex [17]

The 1H NMR spectroscopy complements the structuralinformation of 1 The enol proton observed at 1427 ppm forCPDT ligand disappears in the spectrum of 1 In general therest of the signals are upfield-shifted compared to the ligandexcept SMe protons which are not significantly affected bycoordination (263 ppm in CPDT) The multiplets at 187246 and 266 ppm assigned to cyclopentene moiety are lessshifted from the ligand (at 189 268 and 281 ppm in ligandΔ120575 = minus002 minus022 and minus015 ppm resp) due to the increaseof electron delocalization by the coordination

The chloroform UVndashvis spectrum of 1 (Figure 1) showselectronic transitions in both UV and visible part of thespectrum (Table 1) In the UV range two main absorptionbands are observed corresponding to a ligand transitionOverall the absorption bands are blue shifted respectingligand by the nickel coordination The band at 280 nm wasassigned to the 120587lowast larr 119899 transition of the oxygen atomThe band assigned to 120572 120573-unsaturated system centered at315 nm has an important hyperchromic effect evidencingthe increase of 120587-conjugation in 1 The band at 337 nm wasassigned to a 120587lowast larr 119899 transition of dithiocarbonyl group Twobands on the visible region at 383 and 445 nm may belongto S-Ni and O-Ni LMCT transitions [18 19] In the solidelectronic spectrum the deconvoluted signal centered at 350was assigned to a 120587lowast larr 119899 transition of dithiocarbonyl group

250 300 350 400 450 500 550

Wavenumber (nm)

Abso

rban

ce (a

u)

1

2

Figure 1 Absorption spectra of chloroform solution of 1 and 2 inchloroform

(Figures S1ndashS6 in Supplementary Material available onlineat httpsdoiorg10115520177623210) and S-Ni and O-NiLMCT transitions were observed at 399 and 449 nm and anadditional band appears around 405 nm among two weakerbands at 501 and 714 nmwhichwere assigned to 1A2g larr

1A1gand 1B1g larr

1A1g corresponding to a square planar geometryon nickel(II) center [20 21]

The XPS spectrum of 1 shows the presence of carbonoxygen sulfur and nickel signals (Figure 2 and Table 2)The Ni 2p32 signal at 85487 eV (Table 1) could be assignedto a nickel(II) atom surrounded by OS-donors similarto the reported [Ni(SC(SCH3)CHC(C6H5)O)2] complex(85500 eV) [22] The absence of satellite peaks confirms thediamagnetic behavior of nickel center and the square planargeometry of the complex


Table 2 Binding energies (eV) of the different components observed in XPS spectra for 1 and 2

BE (eV) 1 2 Corresponding peakO 1s 53038 53029 O=C

53199 53192 O-CS 2p 16112 16090 S=C 2p32

16204 16181 S=C 2p1216306 16275 S-C 2p3216411 16382 S-C 2p12

Ni 2p 85487 85501 Ni 2p 32

02004006008001000

＋

Ｃ2０12

Ｃ2０32

＋1３

1３

Ｃ－－Ｃ－－

Ｃ－－

３2３３2０

Ｃ3０

Bonding energy (eV)

Figure 2 Wide-scan XPS spectrum of [Ni(cpdt)2] complex

The S 2p band region shows a single broad peak in 162 eVwith a FWHM= 26 eV by the presence of the 2p12 and 2p32core levels as well as two different sulfur atoms expected bythe ligand structure (Table 2) The peak separation of eachS 2p peak is about 092 and 106 eV The peaks at 16112 and16306 correspond to the 2p32 core level and correspond toS-C and S=C respectively The O 1s spectrum shows a broadpeak centered at 530 eV with a FWHM = 29 eV being inaccord with the presence of more than one species Gaussiandeconvolution of O 1s spectrum shows two peaks at 5301 and5313 eV (Table 2) which were assigned to a O-C and O=Cmoieties respectively Ketoenolate resonance is proved by thepresence of these peaks and the same intensity of both givesfurther evidence of 120587-delocalization on the chelated ring

32 Preparation of 2 One-dimensional coordination poly-mer was obtained in a straightforward process from thesynthesis of 1 and bpy in chloroform media The colorchange from orange to light yellow was the initial evidenceof its presence The FTIR spectrum of 2 shows the signalsassociated with bpy bridge at 2954 1575 1483 1375 and625 cmminus1 towards low wavenumbers respecting the freeligand due to the nickel coordinationThe vibrational energydecreases probably due to the slight electron density fromthe 120590-donation of the bpy When the UVndashvis spectra of 1and 2 in CHCl3 were compared (Figure 1) both of themcontain the same bands with a general hypochromic effecton the former associated with the coordination of the bpymolecule The main changes were in the visible region witha blue shift of LMCT band at 379 nm respecting those of 1(383 nm) The slight decrement of the LMCT energy comes

200 300 400 500 600 700 800 900 1000 1100

Wavenumber (nm)

1

2

lowastlowast

lowast

lowast

re

flect

ance

Figure 3 Absorption spectra of 1 and 2 by Diffuse Reflectancespectroscopy lowastsystematic signals associated with the nature of thespectrophotometer

from the minor molecular orbital energy associated withthe metal center from the pyridine coordination The solidspectrum shows a notable difference respecting precursor(Figure 3) The band LMCT at 459 nm is notably red shiftedfrom 1 (449 nm) similar to similar systems [23] Threemore bands were observed at 571 886 922 and 955 nmwhich were assigned to the transitions 3T1g(P) larr

3A2g(]1)3T1g(F) larr

3A2g(]2) and3T2g(F) larr

3A2g(]3) respectivelyin an octahedral environment around the nickel ion [24ndash28]due to the coordination of two bipyridyl molecules

The XPS spectrum of 2 (Table 2) shows the decrease onS 2p binding energies respecting 1 complex (Table 2) due tothe small nuclear effective charge of the sulfur atom with bpycoordination The 2p32 nickel signal shows a slight increaseon BE with bpy coordination this might be due to a decreaseof its electron density These facts could be related to the 120587-back donation of nickel to S-donor ligand for the N-donorligand attached to metal center

No crystals of 1 and 2 suitable for single crystal wereobtained but PXRD analyses were performed The powderpattern of 2 has a different phase than those observed for bpyand 1 (Figure 4) confirming a new phase different to thoseThediffractogramof 1 shows broader peaks probably due to aless ordered solid than those narrow peaks of 2 which couldbe associated with a higher ordered solid structure


Inte

nsity

(au

)

10 15 20 25 30 35 40 45 5052 theta (degrees)

2

1

bpy

Figure 4 X-ray powder diffractograms of 1 and 2 The mixture of 1and bpy phases is not observed in the polymer diffraction pattern

100 200 300 400 500

Magnetic field (mT)

g = 214

Figure 5 ESR spectra at 300K of powdered sample of 1

The ESR analysis of 2 displays a broad singlet centered at119892 = 214 (Figure 5) corresponding to a paramagnetic centerof nickel(II) [29 30] The line shape of the wide spectrum isassociated with Ni (II) centers with 119904 = 1 [31] and magneticinteractions among them are present [32] Wide endings ofthe spectrum show that the interactions are present evenbefore applying the magnetic field and at higher frequenciesthan the allowed for the ESR spectrometer

The polymeric structure of 2 was confirmed by its mag-netic behavior Figure 6 shows the temperature dependenceof magnetic susceptibility of 2 at 1000Oe applied field Thevalues of magnetic susceptibility slightly increase with thedecrease of the temperature from 300 to 34K The magneti-zation is drastically enhanced below 30K showing a ten-dency towards a lower antiferromagnetism at lower tempera-turesThemagnetization at high temperatures strongly agreeswith Curie-Weiss law as could be seen in 1120594 versus 119879 curve(Figure 6) [33] The fitting result has 120579 = minus99K and 119862= 0375Kmolminus1 values The negative value of 120579 suggests anantiferromagnetic behavior of 2 A 119869 value was calculatedthrough the Weiss constant using the molecular-field theory(MFT) [33] affording an average coupling constant 119869 =minus863 cmminus1 when 119904 = 1 and 119911 = 6 (coordination magneticnumber) were used

The temperature dependence of the effective magneticmoment (Figure 7) shows at 300K a value of 120583eff = 152 120583119861which is lower than those spin only values calculated for119904 = 12 (173 120583119861) and 119904 = 1 (283 120583119861) confirming the antifer-romagnetic behavior of the polymer The value of 120583effdecreases linearly as the temperature decrease up to sim35K Atthis point 120583eff increases with temperature up to a maximum

0 25 50 75 100 125 150 175 200 225 250 275 300

minus1

0

5

10

15

20

25

30

35

40

45

50

55

60

65

times10

minus3

(em

um

ol)

0

100

200

300

400

500

600

700

800

900

1100

1000

minus1

(mol

em

u)

c (emumol)

Figure 6 Temperature dependence of 120594 for 2 (filled circles) andCurie plot (open circles) with the best fit to Curie-Weiss law (dottedline) at 1000Oe applied field

090

095

100

105

110

115

120

125

130

135

140

145

150

155

160ff

(B

)

ff

(B

)

0 25 50 75 100 125 150 175 200 225 250 275 300

T (K)

T (K)

08091011121314

0 10 20 30 40 50

Figure 7 Effective magnetic moment (120583eff ) versus T for 2 at amagnetic field of 1000Oe

at sim12 K decreasing at the lowest temperatures This is atypical antiferromagnetic exchange behavior with a Neeltemperature at 12 K

4 Conclusions

The coordination compound 1 was obtained following thereported methodology The spectroscopy characterizationallows us to propose in a square planar conformation feasibleto prepare a 1D coordination polymer bridging by bpy Thecomplex shows electron delocalization over the chelated ringand a diamagnetic behavior as seen in XPS analyses Thestraightforward synthesis of the polymer yields a compoundwith different physicochemical and structural properties thaninitial complex In solution compared to in solid state theCP was stable and the solid has a different phase than the


precursor complex The paramagnetism of 2 is establishedat 119879 gt 100K These results aim to propose the bridge ofbipyridyl molecules within 1 confirming the presence of a 1Dcoordination compound Importantly further crystallizationtechniques are in progress to confirm themolecular structureof the polymers 1 and 2

Conflicts of Interest

The authors declare that there are no conflicts of interestregarding the publication of this article

Acknowledgments

This research was supported by project SIEA-UAEMex 35762013 and scholarship (Ricardo Rosas-Reyes) by CONACYTno 364553 The authors thank the invaluable technical assis-tance of Professor Roberto Escudero Nieves Zavala-SegoviaAlejandra Nunez-Pineda Lizbeth Triana-Cruz GustavoLopez-Tellez and Citlali Martınez-Soto Thanks are due toDr Samuel Hernandez-Anzaldo for the English revision ofthe manuscript

References

[1] R J Kuppler D J Timmons Q-R Fang et al ldquoPotential appli-cations of metal-organic frameworksrdquo Coordination ChemistryReviews vol 253 no 23-24 pp 3042ndash3066 2009

[2] J Lee O K Farha J Roberts K A Scheidt S T Nguyen andJ T Hupp ldquoMetal-organic framework materials as catalystsrdquoChemical Society Reviews vol 38 no 5 pp 1450ndash1459 2009

[3] D Farrusseng S Aguado and C Pinel ldquoMetal-organic frame-works Opportunities for catalysisrdquo Angewandte Chemie Inter-national Edition vol 48 no 41 pp 7502ndash7513 2009

[4] S Shimomura S Bureekaew and S Kitagawa ldquoMolecular Net-works SE - 8rdquo inMolecular Networks SE - 8 MWHosseini Edpp 96ndash106 Springer Berlin Heidelberg 2009

[5] S Horike S Shimomura and S Kitagawa ldquoSoft porous crys-talsrdquo Nature Chemistry vol 1 no 9 pp 695ndash704 2009

[6] A Morozan and F Jaouen ldquoMetal organic frameworks forelectrochemical applicationsrdquo Energy amp Environmental Sciencevol 5 no 11 pp 9269ndash9290 2012

[7] D V Soldatov P Tinnemans G D Enright C I Ratcliffe PR Diamente and J A Ripmeester ldquoModified metal dibenzoyl-methanates for soft supramolecular materials Extension to oli-gomeric and polymeric host receptors with nanosized voidspacesrdquo Chemistry of Materials vol 15 no 20 pp 3826ndash38402003

[8] M Hanack S Deger and A Lange ldquoBisaxially coordinatedmacrocyclic transition metal complexesrdquo Coordination Chem-istry Reviews vol 83 no C pp 115ndash136 1988

[9] H Schultz H Lehmann M Rein and M Hanack ldquoPhthalo-cyaninatometal and related complexes with special electricaland optical propertiesrdquo in Metal Complexes with TetrapyrroleLigands II SE - 2 J W Buchler Ed vol 74 of Structureand Bonding pp 41ndash146 Springer Berlin Heidelberg BerlinHeidelberg Germany 1991

[10] M Zinic J L Atwood and J W Steed Encyclopedia of Supra-molecular Chemistry pp 1139ndash1149 Marcel Dekker New YorkNY USA 2004

[11] J P Collman J T McDevitt G T Yee et al ldquoConductive poly-mers derived from iron ruthenium and osmium metallopor-phyrinsThe shish-kebab approachrdquo Proceedings of the NationalAcadamy of Sciences of the United States of America vol 83 no13 pp 4581ndash4585 1986

[12] D V Soldatov ldquoSoft organic and metal-organic frameworkswith porous architecture From wheel-and-axle to ladder-and-platform design of host moleculesrdquo Journal of Chemical Crystal-lography vol 36 no 11 pp 747ndash768 2006

[13] J Yoshida S-I Nishikiori and R Kuroda ldquoFormation of 1D and 3 D coordination polymers in the solid state inducedby mechanochemical and annealing treatments bis(3-cyano-pentane-24-dionato) metal complexesrdquo Chemistry (Weinheiman der Bergstrasse Germany) vol 14 no 34 pp 10570ndash105782008

[14] Y-B Dong J-PMaMD Smith et al ldquoOne-dimensional coor-dination polymers generated from an oxadiazole-containingNN1015840-bipyridine-type ligand and Cu(II) saltsrdquo Solid State Sci-ences vol 5 no 4 pp 601ndash610 2003

[15] G Dorange R Kergoat and J E Guerchais Bulletin de LaSociete Chimique de France 11 vol 11 p 3835 1969

[16] R Mayer and H Hartmann ldquoSchwefelheterocyclen und Vor-stufen XXXVIII Reaktionsweise des Trimethylentrithions(45-Dihydro-6H-cyclopenta[d]12-dithiolthions-(3)) und sein-er Salzerdquo Chemische Berichte vol 97 no 7 pp 1886ndash1895 1964

[17] I Garcıa-Orozco M C Ortega-Alfaro J G Lopez-Cortes RA Toscano and C Alvarez-Toledano ldquoSynthesis and character-ization of novel dinuclear copper(I) complexes Dimerizationof [CuL(PPh3)2] (L = methyl 3-hydroxy-3-(p-R-phenyl)-2-pro-penedithioate)rdquo Inorganic Chemistry vol 45 no 4 pp 1766ndash1773 2006

[18] M Asadi K Mohammadi S Esmaielzadeh B Etemadi and HK Fun ldquoSome new Schiff base ligands giving a NNOS coordi-nation sphere and their nickel(II) complexes Synthesis char-acterization and complex formationrdquo Polyhedron vol 28 no 8pp 1409ndash1418 2009

[19] A R Latham V C Hascall and H B Gray ldquoThe electronicstructures and spectral properties of the square-planar dithio-oxalate complexes of Nickel(II) Palladium (II) Platinum (II)and Gold (III)rdquo Inorganic Chemistry vol 4 no 6 pp 788ndash7921965

[20] WRMason III andH BGray ldquoElectronic structures of square-planar complexesrdquo Journal of the American Chemical Societyvol 90 no 21 pp 5721ndash5729 1968

[21] S S Konstantinovic B C Radovanovic Z Cakic and VM Vasic ldquoSynthesis and characterization of Co(II) Ni(II)Cu(II) and Zn(II) complexes with 3-salicylidenehydrazono-2-indolinonerdquo Journal of SerbianChemical Society vol 68 no 8-9pp 641ndash647 2003

[22] L Beyer R Kirmse J Stach R Szargan and E Hoyer ldquoMetal-lkomplexe des Benzoyldithioessigsauremethylesters und desN-Benzoylamino-dithiokohlensaureethylesters Darstellungund Charakterisierung ESCA- und EPR-Untersuchungen [1]rdquoZAAC - Journal of Inorganic and General Chemistry vol 476Zeitschrift Fur Anorganische Und Allgemeine Chemie no 5pp 7ndash15 1981

[23] O Rotthaus F Thomas O Jarjayes C Philouze E Saint-Aman and J-L Pierre ldquoValence tautomerism in octahedral andsquare-planar phenoxyl-nickel(II) complexes Are imino nitro-gen atoms good friendsrdquo Chemistry - A European Journal vol12 (Weinheim an Der Bergstrasse Germany) no 26 pp 6953ndash6962 2006


[24] M G Babashkina D A Safin K Robeyns and YGarcia ldquoA neutral 1D coordination polymer constructedfrom the niii complex of the n-phosphorylated thioureaphnhc(s)nhp(o)(oph)2 and pyrazine A single-source precursorfor nickel nanoparticlesrdquo European Journal of InorganicChemistry vol 2015 no 7 pp 1160ndash1166 2015

[25] N H Al-Shaalan ldquoSynthesis characterization and biologicalactivities of Cu(II) Co(II) Mn(II) Fe(II) and UO 2(VI) com-plexes with a new Schiff base hydrazone O-hydroxyaceto-phenone-7-chloro-4-quinoline hydrazonerdquo Molecules vol 16no 10 pp 8629ndash8645 2011

[26] K B Gudasi S A Patil R S Vadavi R V Shenoy and M SPatil ldquoSynthesis and spectral studies of Cu(II) Ni(II) Co(II)Mn(II) Zn(II) and Cd(II) complexes of a newmacroacyclic lig-and NN1015840-bis(2- benzothiazolyl)-26-pyridinedicarboxamiderdquoJournal of the Serbian Chemical Society vol 71 no 5 pp 529ndash542 2006

[27] R Srinivasan I Sougandi R Venkatesan and P S RaoldquoSynthesis and room temperature single crystal EPR studies of adinickel complex having anNi2(120583-phenoxide)

2+

2unit supported

by a macrocyclic ligand environment [Ni2(L)2(OClO3)2] [L =2-[(4-methyl-pyridin-2-ylimino)-methyl]-phenol]rdquo Journal ofChemical Sciences vol 115 no 2 pp 91ndash102 2003

[28] D Coucouvanis and J P Fackler Jr ldquoSquare-planar sulfur com-plexes VI Reactions of bases with xanthates dithiocarbamatesand dithiolates of nickel(II)rdquo Inorganic Chemistry vol 6 no 11pp 2047ndash2053 1967

[29] M Dey J P Chinta G J Long and P Rao ldquoSynthesis andcharacterization of complexes of Fe(III) Co(III) Ni(II) Cu(II)Zn(II) and UO2+

2with p-tert-butylcalix[4]arene bearing two

iminependants linked through salicylylmoiety at thelower rimrdquoIndian Journal of Chemistry vol 48A no 11 pp 1484ndash14912009

[30] G Bai P Wei and D W Stephan ldquoA 120573-diketiminato-nickel(II)synthon for nickel(I) complexesrdquo Organometallics vol 24 no24 pp 5901ndash5908 2005

[31] F T Vieira G M de Lima J L Wardell S M S V WardellK Krambrock and A F D C Alcantara ldquoSynthesis and cha-racterization of [chloro2(1H)-pyridinethione-Stris(pyridin-2-ylthiolato)methyl-CNN1015840N10158401015840]nickel(II)][Ni(TPTM)(SPyH)Cl]rdquo Journal of Organometallic Chemistryvol 693 no 11 pp 1986ndash1990 2008

[32] IMKrygin andAD Prokhorov ldquoSpin-spin interaction ofNi2+ions in ZnSiF6sdot6H2Ordquo Physics of the Solid State vol 41 no 9 pp1469ndash1475 1999

[33] R L Carlin Magnetochemistry Springer Berlin HeidelbergBerlin Heidelberg Germany 1st edition 1986

Submit your manuscripts athttpswwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 201

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polymer bridged by bpy The structure of the latter wasevidenced by spectroscopy in solid state being unstable insolution

2 Experimental Section

21 Materials and Methods Cyclopentanone methyl iodidepotassium tert-butoxide 441015840-bipyridyl (Aldrich) carbondisulfide and nickel(ii) chloride (J T Baker) were usedwithout further purification Solvents were distilled beforeuse Melting points were determined in a Melt-temp II 1Hand 13CNMR spectra were recorded using a Bruker-Advance300MHz spectrometer using TMS as internal standard IRspectra were recorded on a Nicolet Avatar 360 in KBr andATR FT-IR Shimadzu IR Prestige-21 model with 4 cmminus1 ofresolution Electronic absorption spectra were obtained on aPerkin Elmer lambda 25 spectrophotometerThe XPS spectrawere acquired using a JEOL JPS-9200 equipped with a MgX-ray source (12536 eV) at 200W the area of analysis was1mm and the vacuum was in the order of 10minus8 Torr forall samples The spectra were analyzed using the SpecSurfsoftware included with the instrument all spectra werecharge-corrected using the carbon signal (C 1s) at 2845 eV asa referenceThe Shirley method was used for the backgroundsubtraction while in the curve fitting process the Gauss-Lorentz method was used Electron Paramagnetic Resonancespectra were recorded on JOEL JES-TE300 of 14 T spectrom-eter operated on X-band at FM 100KHz in cylindrical cavityon TE011 method The samples were handled as solid intoWilmad quartz tubes Magnetization measurements wereperformed with a Quantum Design MPMS SQUID magne-tometerMPMS-5 Field-cooling (FC) cycle was performed atmagnetic field intensity of 1000Oe in the range 2 up to 300KPowder X-ray diffraction data were acquired in a Bruker D8advance diffractometer equipped with a Linxeye detectorusing Ni-filtered Cu K120572 radiation Tube conditions were30 kV 30 mA 2120579 range 5ndash50∘ step size 002∘ step time 32 s

22 Synthesis of the Methyl 2-Hydroxycyclopent-1-encarbod-ithioate Ligand (CPDT) To potassium tert-butoxide (83 g74mmol) in 200mL of dry ethyl ether was added cyclopen-tanone (3mL 34mmol) under stirring at minus10∘C After 30minutes a solution of CS2 (22mL 36mmol) in the samesolvent (20mL) was added continuing the stirring for 15 hmore Methyl iodide (22mL 36mmol) was then added anda reddish suspension was obtainedThe solvent was removedunder vacuum the solid was dissolved in water and acidifiedwith HCl 2M extracted with CH2Cl2 dried by Na2SO4and concentrated A yellow crystalline solid was obtainedby silica-gel chromatography using hexane as eluent Yield315 g (53) mp 376∘C IR (KBr cmminus1) 3427 br 2924m2853m 1644w 1553 s 1523m 1447m 1423w 1330w 1242m1072w 1020w 984w 949w 789w IR (ATR cmminus1) 2953w2915 w 2851 w 1547 s 1443m 1418m 1237m 793m 1HRMN (300MHz CDCl3) 120575 189 (q 2H 119869 = 74 79HzCH2CH2CH2) 263 (s 3H SCH3) 267 (t 2H 119869 = 79HzCH2CH2C=) 280 (t 2H 119869 = 74Hz C(O)CH2CH2) 1427 (1199041H OH) 13C NMR (75MHz CDCl3) 120575 1679 (SCH3) 1839

HOO OS

SS S

SS

2

1CPDT

NiNaOHNiCＦ2

EtOH

Scheme 1 Synthesis of 1 from CPDT ligand

(CH2CH2C=) 3079 (CH2CH2CH2) 3507 (C(O)CH2CH2)11930 (Cvin) 17947 (CO) 21363 (CS2) UVndashVis (CHCl3)[120582max nm (120576 Mminus1 cmminus1)] 319 (17650) 354 (13450) 374(17160)

23 Synthesis of bis-[Methyl 1-Hydroxy-1-cyclopentene-2-di-thiocarboxylate-OS]nickel(II) 1 An aqueous NaOH solution(5mL 04M) was added to a warm ethanolic solutionof CPDT (034 g 195mmol) under stirring NiCl2sdot6H2O(024 g 099mmol) in 25mL of ethanol was then addedto the mixture producing an orange solid The precipitatewas filtered and washed with ethanol and hexane yielding034 g (87) mp d250∘C Calc for C14H18NiO2S4sdotH2O C3973 H 476 S 3030 Found C 3989 H 431 S 3016IR (KBr cmminus1) 2904w 1546 s 1406 s 1287m 972w 934w910m 846w 669w IR (ATR cmminus1) 2951 w 2908w 2863w1545 s 1441 s 1409 s 1288w 847m 1H RMN (300MHzCDCl3) 120575 186 (m 2H 119869 = 76 78Hz CH2CH2CH2) 246(t 2H 119869 = 78Hz CH2CH2C=) 259 (s 3H SCH3) 265 (t2H 119869 = 76Hz C(O)CH2CH2) UVndashVis (CHCl3) [120582max nm(120576 Mminus1 cmminus1)] 238 (28330) 245 (26260) 277 (25350) 313(31160) 334 (25950) 378 (5600) 439 (4190) UVndashVis-NIR(solid) [120582max nm] 405 513 705

24 Synthesis of catena-[(1205832-441015840-Bipyridyl)-bis-(methyl 2-Hy-droxy-1-cyclopentene-2-dithiocarboxylate-OS)nickel(II)] 2 Asolution of bpy (008 g 053mmol) in 10mL of CHCl3 wasadded to a 50mL of chloroform solution of 1 (0104 g025mmol) under stirring at room temperature for 1 h Theyellow solid was filtered washed with CHCl3 and driedunder vacuum Yield 0106 g (73) mp d270∘C Calc forC24H26N2NiO2S4sdot025 CHCl3 C 4999 H 458 S 2201 N481 Found C 4985 H 446 S 2153 N 471 IR (ATRcmminus1) 2874w 2954w 2911 w 2834w 1575m 1483 s 1419 s1375 s 1274m 801m 727m 625m UVndashVis-NIR (solid)[120582max nm] 441 614 876 928 1008

3 Results and Discussion

31 Synthesis and Characterization of 1 1 was obtainedaccording to similar methodology (Scheme 1) previouslyreported for the nickel complexes of the methyl 3-hydroxy-3(41015840-R-phenyl)-2-propenedithiocarboxylate ligands [15]Theproposed structure of 1 was built by its spectroscopic charac-teristics and single crystal analysis

In the IR spectrum of 1 the loss of the centered bandis observed at 3427 cmminus1 which was assigned to H-O enolgroup in the ligand The signals at 1405 and 909 cmminus1 wereassigned to 120575(C-O) These signals were low energy-shifted






501 499714

3T1g(P) larr3A2g(]1) 571

3T1g(F) larr3A2g(]2) 886

3T2g(F) larr3A2g(]3) 934 922




250 300 350 400 450 500 550

Wavenumber (nm)

Abso

rban

ce (a

u)

1

2



1A1gand 1B1g larr






53199 53192 O-CS 2p 16112 16090 S=C 2p32

16204 16181 S=C 2p1216306 16275 S-C 2p3216411 16382 S-C 2p12

Ni 2p 85487 85501 Ni 2p 32

02004006008001000

＋

Ｃ2０12

Ｃ2０32

＋1３

1３

Ｃ－－Ｃ－－

Ｃ－－

３2３３2０

Ｃ3０

Bonding energy (eV)




200 300 400 500 600 700 800 900 1000 1100

Wavenumber (nm)

1

2

lowastlowast

lowast

lowast

re

flect

ance









Inte

nsity

(au

)

10 15 20 25 30 35 40 45 5052 theta (degrees)

2

1

bpy


100 200 300 400 500

Magnetic field (mT)

g = 214





0 25 50 75 100 125 150 175 200 225 250 275 300

minus1

0

5

10

15

20

25

30

35

40

45

50

55

60

65

times10

minus3

(em

um

ol)

0

100

200

300

400

500

600

700

800

900

1100

1000

minus1

(mol

em

u)

c (emumol)


090

095

100

105

110

115

120

125

130

135

140

145

150

155

160ff

(B

)

ff

(B

)

0 25 50 75 100 125 150 175 200 225 250 275 300

T (K)

T (K)

08091011121314

0 10 20 30 40 50



4 Conclusions






Acknowledgments


References





























2+

2unit supported



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






501 499714

3T1g(P) larr3A2g(]1) 571

3T1g(F) larr3A2g(]2) 886

3T2g(F) larr3A2g(]3) 934 922




250 300 350 400 450 500 550

Wavenumber (nm)

Abso

rban

ce (a

u)

1

2



1A1gand 1B1g larr






53199 53192 O-CS 2p 16112 16090 S=C 2p32

16204 16181 S=C 2p1216306 16275 S-C 2p3216411 16382 S-C 2p12

Ni 2p 85487 85501 Ni 2p 32

02004006008001000

＋

Ｃ2０12

Ｃ2０32

＋1３

1３

Ｃ－－Ｃ－－

Ｃ－－

３2３３2０

Ｃ3０

Bonding energy (eV)




200 300 400 500 600 700 800 900 1000 1100

Wavenumber (nm)

1

2

lowastlowast

lowast

lowast

re

flect

ance









Inte

nsity

(au

)

10 15 20 25 30 35 40 45 5052 theta (degrees)

2

1

bpy


100 200 300 400 500

Magnetic field (mT)

g = 214





0 25 50 75 100 125 150 175 200 225 250 275 300

minus1

0

5

10

15

20

25

30

35

40

45

50

55

60

65

times10

minus3

(em

um

ol)

0

100

200

300

400

500

600

700

800

900

1100

1000

minus1

(mol

em

u)

c (emumol)


090

095

100

105

110

115

120

125

130

135

140

145

150

155

160ff

(B

)

ff

(B

)

0 25 50 75 100 125 150 175 200 225 250 275 300

T (K)

T (K)

08091011121314

0 10 20 30 40 50



4 Conclusions






Acknowledgments


References





























2+

2unit supported



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




53199 53192 O-CS 2p 16112 16090 S=C 2p32

16204 16181 S=C 2p1216306 16275 S-C 2p3216411 16382 S-C 2p12

Ni 2p 85487 85501 Ni 2p 32

02004006008001000

＋

Ｃ2０12

Ｃ2０32

＋1３

1３

Ｃ－－Ｃ－－

Ｃ－－

３2３３2０

Ｃ3０

Bonding energy (eV)




200 300 400 500 600 700 800 900 1000 1100

Wavenumber (nm)

1

2

lowastlowast

lowast

lowast

re

flect

ance









Inte

nsity

(au

)

10 15 20 25 30 35 40 45 5052 theta (degrees)

2

1

bpy


100 200 300 400 500

Magnetic field (mT)

g = 214





0 25 50 75 100 125 150 175 200 225 250 275 300

minus1

0

5

10

15

20

25

30

35

40

45

50

55

60

65

times10

minus3

(em

um

ol)

0

100

200

300

400

500

600

700

800

900

1100

1000

minus1

(mol

em

u)

c (emumol)


090

095

100

105

110

115

120

125

130

135

140

145

150

155

160ff

(B

)

ff

(B

)

0 25 50 75 100 125 150 175 200 225 250 275 300

T (K)

T (K)

08091011121314

0 10 20 30 40 50



4 Conclusions






Acknowledgments


References





























2+

2unit supported



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Inte

nsity

(au

)

10 15 20 25 30 35 40 45 5052 theta (degrees)

2

1

bpy


100 200 300 400 500

Magnetic field (mT)

g = 214





0 25 50 75 100 125 150 175 200 225 250 275 300

minus1

0

5

10

15

20

25

30

35

40

45

50

55

60

65

times10

minus3

(em

um

ol)

0

100

200

300

400

500

600

700

800

900

1100

1000

minus1

(mol

em

u)

c (emumol)


090

095

100

105

110

115

120

125

130

135

140

145

150

155

160ff

(B

)

ff

(B

)

0 25 50 75 100 125 150 175 200 225 250 275 300

T (K)

T (K)

08091011121314

0 10 20 30 40 50



4 Conclusions






Acknowledgments


References





























2+

2unit supported



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





Acknowledgments


References





























2+

2unit supported



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






2+

2unit supported



















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

synthesis of a one-dimensional coordination polymer of

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