Syntheses,Structures and DNA Interaction of Zn(Ⅱ)and Pb(Ⅱ)Complexes Based on Imidazo-phenanthrolin-phenoxy Acetic Acid

SHEN WeiHU Wei-JiWU Xiao-YongZHAO Guo-Liang

(1College of Chemistry and Life Science,Zhejiang Normal University,Jinhua,Zhejiang 321004,China)

(2Xingzhi College,Zhejiang Normal University,Jinhua,Zhejiang 321004,China)

Syntheses,Structures and DNA Interaction of Zn(Ⅱ)and Pb(Ⅱ)Complexes Based on Imidazo-phenanthrolin-phenoxy Acetic Acid

SHEN Wei1HU Wei-Ji1WU Xiao-Yong1ZHAO Guo-Liang＊,,2

(1College of Chemistry and Life Science,Zhejiang Normal University,Jinhua,Zhejiang 321004,China)

(2Xingzhi College,Zhejiang Normal University,Jinhua,Zhejiang 321004,China)

Two novel complexes[Zn(PIMPHC)2]n(1),{[Pb(OIMPHC)2]·4H2O}n(2)were synthesized under hydrothermal reactions by using 2-(4-(1H-imidazo-2-[4,5-f][1,10]phenanthrolinyl)phenoxy)acetic acid(HPIMPHC)and 2-(2-(1H-imidazo-2-[4,5-f][1,10]phenanthrolinyl)phenoxy)acetic acid(HOIMPHC).Complex 1 crystallizes in orthorhombic system with space group Pbcn.Zn(Ⅱ)is six-coordinated by two PIMPHC-anions,forming a distorted octahedral coordination geometry.Complex 2 crystallizes in monoclinic system with space group P21/n,Pb(Ⅱ)is seven-coordinated,forming a distorted pentagonal bipyramid coordination geometry.The fluorescence spectra indicate that the interaction of the complexes with DNA are stronger than ligands.CCDC:1476033,1;1476034,2.

2-(4-(1H-imidazo-2-[4,5-f][1,10]phenanthrolinyl)phenoxy)acetic acid;2-(2-(1H-imidazo-2-[4,5-f][1,10]phenanthrolinyl) phenoxy)acetic acid;Zn(Ⅱ);Pb(Ⅱ);DNA-binding

Rational designs and syntheses of coordination polymers have attracted great interests in recent decades,owing to their rich structural aesthetics[1-5]and functionalities[6-9].According to some factors of formation,molecularstructuresandpropertiesof coordination polymers can be speculated,such asmetal ions(nodes),ligands(linkers),metal-ligand ratio,supramolecular interaction,reaction conditions. Therefore,itispossibletodevelopatargeted architecture through the choice of organic ligands and metal ions.

So far,extensive work has been carried out by using heterocycliccarboxylate ligands[10-17],because these ligands containing both N-and O-donors are good choices to build multi-configurations.Carboxylate groups often play important roles in many organic ligands,which have different coordinating modes, such as monodentate terminal,bidentate bridging, bidentate chelating modes.The coordination modes make the expected structures much more robust.What is more,the flexibility of carboxylate groups offers the possibilities to form different topologies.Deprotonated carboxylategroupscanformhydrogenbondsto participateinsupermolecularself-assemblywith coordination bonds as acceptors.Heterocyclic rings are expected to show robust coordination modes in the construction，andtheπ-πstackinginteractions between heterocyclic rings make the whole framework further stable.

Asismentionedabove,theadvantagesof heterocyclic carboxylate ligands offer a self-assembly solution that can be expected and controlled in certain extent.In this paper,two novel ligands(2-(4-(1H-imidazo-2-[4,5-f][1,10]phenanthrolinyl)phenoxy)acetic acid(HPIMPHC)and 2-(2-(1H-imidazo-2-[4,5-f][1,10] phenanthrolinyl)phenoxy)acetic acid(HOIMPHC))were designed and synthesized,thereby two novel complexes ([Zn(PIMPHC)2]n(1),{[Pb(OIMPHC)2]·4H2O}n(2))were synthesized by hydrothermal reaction method.The interaction between complexes,ligands and ct-DNA were studied by EtBr fluorescence probe.

1 Experimental

1.1 Chemical and materials

All of the reagents were of analytical grade and used without further purification.Calf thymus DNA (ct-DNA)was prepared with 0.1 mol·L-1NaCl.The concentration of ct-DNA was 200 μg·mL-1(cDNA= 3.72×10-4mol·L-1).The ct-DNA solutions were stored at 4℃and gave a ratio of UV-Vis absorbance at 260 and 280 nm,A260/A280=1.8,indicating that DNA was sufficiently free of protein.The buffer solution,0.0l mol·L-1Tris-HCl(tris(hydroxymethyl)aminomethane hydrochloride(pH=7.4)),was prepared with doubledistilled water.

ElementalanalysiswasperformedonCHN elemental analyzer,Elementar Vario ELⅢ.FTIR spectra was recorded on a Nicolet NEXUS 670 FTIR spectrophotometer,using KBr discs in the range of 4 000～400 cm-1.Crystallographic data of the complexes were collected on a Bruker Smart ApexⅡCCD diffractometer.A Mettler Toledo thermal analyzer TGA/SDTA 851ewas used to carry out the thermoanalytical analysis with a heating rate of 10℃·min-1from 30 to 800℃in air atmosphere.Fluorescence spectra were measured at room temperature with an Edinburgh FL-FS920 TCSPC system.1H NMR spectra of ligands were acquired with Bruker AV400 NMR instrument in DMSO-d6solution with TMS as internal standard.

1.2 Synthesis of ligands

2-(4-(1H-imidazo-2-[4,5-f][1,10]phenanthrolinyl) phenoxy)acetic acid(HPIMPHC)and 2-(2-(1H-imidazo-2-[4,5-f][1,10]phenanthrolinyl)phenoxy)acetic acid(HOIMPHC)were synthesized according to literature(Fig.1)[18-20].

1.2.1 2-(4-formylphenoxy)acetic acid[18]

Chloracetic acid(2.5 mL,50%)was added to 4-hydroxybenzaldehyde(1 g)and NaOH solution(3.5 mL,33%),and gently heated on water bath(80℃)for 1 h.Then the mixture was immediately acidified with concentratedHCl,extractedwithetherand5% Na2CO3solution.Na2CO3extract was acidified with concentrated HCl.White powder was isolated and separated by filtration.The product thus obtained was recrystallized from ethanol.Yield:86%.

1.2.2 1,10-phenanthroline-5,6-dione[19]

1,10-phenanthroline(1.20 g,6 mmol)was added to concentrated H2SO4(20 mL)and concentrated HNO3(10 mL)at 0℃.The mixture was refluxing at 80℃for 2 h,then cooled to room temperature.The contents were diluted with deionized water(400 mL),and neutralized with NaHCO3,then extracted with methylene chloride,and dried over anhydrous Na2SO4. Yellow-brown powder was obtained.Yellow-brown crystals were recrystallized from methanol.Yield: 90%.

Fig.1Synthesis of HPIMPHC and HOIMPHC

1.2.32 -(4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenoxy)acetic acid(HPIMPHC)[20]

1,10-phenanthroline-5,6-dione(5 mmol,1.05 g) and 2-(4-formylphenoxy)acetic acid(5 mmol,0.90 g) were added in the NH4Ac-HAc buffer solution(10%, 20 mL).The mixture was heated in the open flask at 80℃.Deionized water was required to control the volume of solution.Yield:80%.Anal.Calcd.for C21H13N4O3(%):C,68.29;H,3.54;N,15.17;Found (%):C,68.25;H,3.58;N,15.23.IR(KBr,cm-1):3 418 (br),2 358(w),1 611(s),1 579(m),1 559(m),1 538 (m),1484(m),1 458(m),1 422(m),1 362(w),1 338(w), 1 315(w),1 295(w),1 254(m),1 190(m),1 127(w), 1 059(m),958(w),846(w),822(w),742(w),721(m), 694(w).1H NMR(400MHz,DMSO-d6):δ 8.90～9.03 (4H)for phenanthroline-H,7.83～7.84(2H)for phenanthroline-H,7.17～7.19(2H)for benzene-H,8.21～8.23 (2H)for benzene-H,4.83(2H,s,-CH2-),13.66(H,-OH).

1.2.32 -(2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenoxy)acetic acid(HOIMPHC)

The synthetic process of HOIMPHC is the same as HPIMPHC.2-hydroxybenzaldehyde was used instead of 4-hydroxybenzaldehyde.Yellow-brown powder was recrystallized from methanol.Yield:70.1%,Anal. Calcd.for C21H13N4O3(%):C,68.29;H,3.54;N,15.17; Found(%):C,68.22;H,3.53;N,15.32.IR(KBr,cm-1): 3 440(br),2 362(w),1 680(s),1 584(m),1 562(m),1 544 (m),1488(m),1 462(m),1 433(m),1 375(w),1 345(w), 1 323(w),1 294(w),1 252(m),1 195(m),1132(w),1 065 (m),959(w),841(w),805(w),752(w),735(m),704(w).1H NMR(400 MHz,DMSO-d6):δ 8.42～8.94(4H)for phenanthroline-H,7.73～7.79(2H)for phenanthroline-H,7.15,7.24,7.51,7.76(4H)for benzene-H,4.76(2H, s,-CH2-),14.45(H,-OH).

1.3 Synthesis of complexes

[Zn(PIMPHC)2]n(1):A mixture of HPIMPHC (0.148 g,0.4 mmol),NaOH(0.016 g,0.4 mmol),ZnSO4·7H2O(0.058 g,0.2 mmol),and H2O/EtOH(20 mL,1∶1,V/V)was sealed in a 25 mL Teflon-lined stainless steel vessel and heated at 160℃for 3 d.Then the mixture was cooled to room temperature at a rate of 10℃·h-1,with colorless crystals appearing at the bottomoftheTeflonvessel.Afterwashedwith distilled water and dried in air,the crystals suitable for single-crystal analysis and physical measurements were obtained.Yield:45%(based on HPIMPHC). Anal.Calcd.for C42H26N8O6Zn(%):C,62.68;H,3.23; N,13.93;Found(%):C,62.54;H,3.19;N,13.87;IR (KBr,cm-1):3 072(w),2 354(w),1 608(s),1 527(m), 1 479(s),1 454(m),1 362(m),1 075(m),837(m),812 (m),733(m),694(m),635(m).

{[Pb(OIMPHC)2]·4H2O}n(2):The preparation of 2 was similar to 1 using HOIMPHC and Pb(NO3)2instead of HPIMPHC andYield:38%(based on HOIMPHC).Anal.Calcd.for C42H34N8O10Pb(%):C, 49.51;H,3.34;N,11.00;Found(%):C,49.40;H, 3.29;N,10.96;IR(KBr,cm-1):3 424(w),2 361(w),1 607(s),1 514(s),1 481(s),1 446(m),1 388(m),1 358(m), 1 259(m),1 224(m),1 067(m),836(m),817(m),740 (m),701(m),638(m).

1.4 Single X-ray crystallographic study

The single crystal of the complexes with approximate dimensions were mounted on a Bruker Smart Apex CCD diffractometer.A graphite monochromated Mo Kα radiation(λ=0.071 073 nm)was used to collect the diffraction data at 296 K.The structures were solved by SHELXS-97 program package[21-22]and refined with the full-matrix least-squares technique based on F2using the SHELXTL-97 program package[23].All non-H atoms were anisotropically refined.Remaining hydrogen atoms were added in calculated positons and refined as riding atoms with a common fixed isotropic thermal parameter.Hydrogen atoms on water molecules were located in a difference Fourier map and included in the subsequent refinement using restrains(d(O-H)= 0.085 nm)with Uiso(H)=1.5 Ueq(O).Detail information about the crystal data is summarized in Table 1. Selected interatomic distances and bond angles are given in Table 2 and Table 3.

CCDC:1476033,1;1476034,2.

Table 1Crystallographic data for complex 1 and complex 2

Table 2Selected bond lengths(nm)and angle(°)for 1

Continued Table 2

Table 3Selected bond lengths(nm)and angle(°)for 2

2 Results and discussion

2.1 Crystal structure of[Zn(PIMPHC)2]n(1)

Single-crystal analysis shows that 1 crystallizes in orthorhombic system with space group Pbcn.The asymmetric unit cell contains one Zn(Ⅱ)ion and two PIMPHC-anions.The Zn(Ⅱ)exhibits distorted sixcoordinatedgeometrybyconsideringshort-range atomic interactions.Each Zn(Ⅱ)is bound to four nitrogen atoms(N1,N2,N1iii,N2iii,Zn-N 0.220 1(2)～0.221 2(3)nm)and two oxygen atoms(O2i,O2ii,Zn-O 0.203 4(2)nm).PIMPHC-adopts a μ2-κO∶κ2N coordination fashion to connect two Zn(Ⅱ)ions.The selected distances and bond angles for complex 1 fall in the normal regions which are comparable to the values reported in literatures[24-26].

Fig.2Coordinated environment of complex 1

Intheμ2-κO∶κ2Ncoordinationfashion,the phenanthroline unit chelates to one Zn(Ⅱ)and the deprotonated carboxylate unit is bound to another. The coordination mode of the μ2-PIMPHC-forms metallacyclic rings,which can be described as a 2D (2,4)-connected binodal network with the Schl?fli symbol of(84·122)2·(8)2.Every plane is parallel to each other.Through π…π stacking interaction of ligands and hydrogen bonds,2D polymers form 3D structures.

2.2 Crystal structure of{[Pb(OIMPHC)2]·4H2O}n(2)

Fig.3(a)Single-layer 2D structure of complex 1;(b)3D packing diagram of complex 1;(c)2D topological structure of complex 1

Single-crystal analysis shows that 2 crystallizes in monoclinic crystallographic system with space group P21/n.The asymmetric unit cell contains one Pb(Ⅱ) ion,two crystallographically independent OIMPHC-anions and four water molecules.The Pb(Ⅱ)exhibits highly distorted seven-coordinated geometry by considering short-range atomic interactions.Each Pb(Ⅱ)is bound to four nitrogen atoms(N1,N2,N3,N4,Pb-N 0.253 5(4)～0.259 2(4)nm)and three oxygen atoms (O2,O4,O5,Pb-O 0.281 4(4)～0.299 8(3)nm)of ligands.OIMPHC-adopts μ2-κO∶κ2N and μ2-κ2O∶κ2N coordination fashions to connect two Pb(Ⅱ)ions.The selected distances and bond angles for complex 2 fall in the normal regions which are comparable to the values reported in literatures[27-32].In μ2-κO∶κ2N coordination fashion,the phenanthroline unit chelates to one Pb(Ⅱ)ion and the deprotonated carboxylate unit is bound to another.In μ2-κ2O∶κ2N coordination fashion, the phenanthroline unit chelates to one Pb(Ⅱ),and the deprotonated carboxylate unit chelates to another. These coordination modes forms metallacyclic rings, which can be described as a 2D(2,2,3)network with the Schl?fli symbol of(83)2·(8).Every plane is parallel to each other.

In the 2D polymers,the coordinating competition between phenanthroline unit and carboxylate unit need to be considered.To simplify the demonstration, the ligand coordinated by one oxygen atom and two nitrogen atoms(O2,N1,N2)is labelled as A,the other as B.The different coordinating modes result in the considerable dihedral anglar difference between the benzeneringandthephenanthrolinering.The dihedral angle of A and B are 0.980°and 5.299°, respectively,which are attributed to different coordinating modes of ligands.One interpretation may be attributedtoπ-πstackinginteractionsbetween conjugate rings of ligands.The distance between adjacent imidazo-phenanthroline rings is 0.337 5 nm. According to Table 3,Bond distances of Pb-O are much longer than usual(Pb1-O2i0.281 6(4)nm,Pb1-O4ii0.299 8(3)nm,Pb1-O5ii0.281 4(4)nm).The long Pb-O bonds can be ascribed to different coordinating modesasfive-memberchelatingmodeismuch stronger than monodentate mode and four-member chelating mode.While the four-member chelating mode still has some effects on the structure,some toision angles(Pb1-N1-C15-C16 23.9(5)°,Pb1-N2-C16-C15-23.1(5)°,Pb1-N3-C35-C36 22.9(5)°,Pb1-N4-C36-C35-20.9(5)°)can be recognized.

Fig.4Coordinated environment of complex 2

Fig.5(a)2D structure of complex 2;(b)Topological structure of complex 2

Fig.6(a)1D water chain of complex 2;(b)Ligands linked via hydrogen bonds;(c)Hydrogen-bonded packing diagram of complex 2

A self-assemble chain of water molecules(O2Wi-H2WAi…O1Wiv,O1W-H1WA…O4W,O4W-H4WA…O2Wi,O4W-H4WB…O1W,O3Wii-H3WBii…O4W) are observed in Table 4.Water chains are fixed by hydrogen bonds(O1W-H1WB…O1iii,O2Wi-H2WBi…O4i,O3Wii-H3WAii…N7ii)and interconnect adjacency 2D networks to form 3D constructures.A side view of the same part of the structure along the direction is shown in Fig.6(c),where water chains parallel to this direction and crossing into the space of 2D networks are clearly seen.

2.3 IR analysis

The stretching vibration of C=O(1 611 cm-1)for HPIMPHC is much smaller than usual[33],which may be owing to intermolecular hydrogen bonds among carboxylate groups.In complex 1,This characteristicstretching vibration of C=O and O-H are absent and the asymmetric and symmetric stretchings of COO-appear at 1 608 cm-1(ν(OCO)asym)and 1 362 cm-1(ν(OCO)sym)respectively,showing the presence of mono -dentate carboxylate linkage.The C=N characteristic stretching vibration of HPIMPHC is 1 483 cm-1,while it shifts to 1 479 cm-1in complex 1.It is concluded that the chelating mode of phenanthroline groups reduces the frequency of C=N stretching vibration.

Table 4Hydrogen bond distances(nm)and angles(°)in complex 2

So is the complex 2,the characteristic stretching vibrations of O-H and C=O for HOIMPHC are absent and the asymmetric and symmetric stretchings of COO-appear at 1 607 cm-1(ν(OCO)asym),1 388 cm-1(ν(OCO)sym) and 1 358 cm-1(ν(OCO)sym)respectively,which shows the presence of two different carboxylate linkage.The carboxylate groups act as both bidenate and monodenate coordination modes.The C=N characteristic stretching vibration of HOIMPHC is 1 483 cm-1,while it shifts to 1 481 cm-1in complex 2,which is similar to complex 1.

2.4 Thermal decomposition of complexes

The TG curves of the title complexes are shown in Fig.7.No weight loss of complex 1 was observed below 200℃,indicating that there is no small solvent molecules in complex 1.The decomposition of complex 1 starts at 200℃and ended at 440℃,and the observed weight loss(89.98%)accompanied with the decomposition of PIMPHC-(Calcd.89.88%).The residual weight 10.02%might correspond to ZnO (Calcd.10.12%).Complex 2 experiences two steps of weight loss.The first step is from 72 to 129℃with a weight loss of 7.17%,which corresponds to the loss of four water molecules(Calcd.7.07%).The second step in the range of 220～527℃with a weight loss of 71.14%corresponds to the decomposition of OIMPHC-(Calcd.71.00%).Finally,the remaining weight of 21.69%,seems likely to correspond to PbO(Calcd. 21.93%).

Fig.7TG curves for complex 1(a)and 2(b)

2.5 EB-DNA binding study by fluorescence spectrum

The effects of the ligands and complexes on the fluorescence spectra of EB-DNA system are presented in Fig.8,the fluorescence intensities of EB bound to ct-DNA at 592 nm show remarkable decreasing trends with the increasing concentration of the complexes, indicating that some EB molecules are released into solution after the exchange with the compounds which resulted in the fluorescence quenching of EB.The quenching of EB bound to DNA by the compounds is in agreement with the linear Stern-Volmer equation: I0/I=1+Ksqr[34],where I0and I represent the fluorescence intensities in the absence and presence of quencher, respectively.Ksqis the linear Stern-Volmer quenchingconstant,r is the ratio of the concentration of quencher and DNA.In the quenching plots(insets in Fig.8)of I0/I versus r,Ksqvalues are given by the slopes.The Ksqvalues for the compounds are 0.270,1.497 for HPIMPC and complex 1,0.318,1.854 for HOIMPC and complex 2,respectively.The results indicate that interaction of the complexes with DNA are stronger than ligands,because the complexes have higher rigidity to bind the base pairs along DNA,thus increasing their binding abilities.

Fig.8Emission spectra of EB-DNA system in the absence and presence of ligands and complexes

3 Conclusions

Insummary,newligandsHPIMPHCand HOIMPHC were purposely synthesized based on 1, 10-phenanthroline.Both of ligands were successfully appliedto constructing[Zn(PIMPHC)2]n(1), {[Pb(OIMPHC)2]·4H2O}n(2).The complex 1 is a 2D framework with(2,4)-connected topology.The complex 2 is a 2D framework with(2,2,4)-connected topology. Because of the competition among monodentate mode, four-member chelating mode and five-member chelating mode,bond distances of Pb-O are much longer than usual.Complex 2 has stronger interaction with DNA, which can release more free EB molecules from EBDNA.

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咪唑-菲咯啉-苯氧乙酸鋅、鉛配合物的合成，結(jié)構(gòu)及與DNA的相互作用

沈偉1胡未極1吳小勇1趙國良＊,1,2
(1浙江師范大學(xué)化學(xué)與生命科學(xué)學(xué)院，金華321004)
(2浙江師范大學(xué)行知學(xué)院，金華321004)

以2-4-(1H-咪唑-2-[4,5-f][1,10]菲咯啉基)苯氧乙酸(HPIMPHC)和2-2-(1H-咪唑-2-[4,5-f][1,10]菲咯啉基)苯氧乙酸(HOIMPHC)為配體，水熱合成了2種新型配合物[Zn(PIMPHC)2]n(1)和{[Pb(OIMPHC)2]·4H2O}n(2)。配合物1屬正交晶系，空間群為Pbcn；Zn(Ⅱ)的配位數(shù)為6，配位構(gòu)型為變形的八面體，形成2D網(wǎng)狀結(jié)構(gòu)。配合物2屬單斜晶系，空間群為P21/n；Pb(Ⅱ)的配位數(shù)為7，配位構(gòu)型為變形的五角雙錐，形成2D網(wǎng)狀結(jié)構(gòu)。熒光光譜的結(jié)果表明，配合物與DNA的相互作用強于配體。

2-4-(1H-咪唑-2-[4，5-f][1，10]菲咯啉基)苯氧乙酸；2-2-(1H-咪唑-2-[4，5-f][1，10]菲咯啉基)苯氧乙酸；Zn(Ⅱ)；Pb(Ⅱ)；DNA作用

O614.24+1；O614.43+3

A

1001-4861(2016)06-1101-10

2016-01-17。收修改稿日期：2016-04-23。

10.11862/CJIC.2016.132

浙江省自然科學(xué)基金(No.LY12B01003)資助項目。

＊通信聯(lián)系人。E-mail：sky53@zjnu.cn