Synthesis, Anticancer And Catalytic Activities Of Novel Mono Nuclear Cu2+, Co2+, And Zn2+ Complexes Involving Benzotriazol, Ethane-1, 2- DiamineAnd 4, 4’- Diaminocyclohexy lmethane Ligands

1. Abstract Inthisstudy, servaleco-friendly novel comple xesweresyn the sized and characterized having the general formula of [CoC46H- Cl N O ](I), [CuCHCl N O ](II), [CuC HCl N O ](III)history. Soriano-García et al. (2007) synthesized 3β-(p-iodobenzoyloxy) 16α, 17α-epoxypregn-4-En-6, 20-dione and used it in the treatment of and rogen-dependent diseases[11]. In2020, Hasijaet al. synthesized, characterized and reported on the scope off uran 60284 4353 273 416 248 and [ClZn, CHN, HO] (IV) usingbenzotriazol, Ethane-1, 2- and naptho-furancons is ting of moleculesin electronic devices 4 1328 2 2 Diamine, and4, 4’-Diaminocy clohexyl methaneas ligands through one-pot method using anhydrous methanol or ethanol with different metal salt (2:1 eqv) metal to ligand stoichiometry. The crystal structures of these complexes were determined by X-ray diffraction and further characterized by elemental analysis, ESIMS, IR, NMR and UV‒Vis. Single-crystal XRD studies shows that the structural diversities are mainly affected and controlledbythetypesofcentralmetalions.

2. Introduction Coordination complexes have many medicinal, industrial and other pharmacological applications, such as anti-cholesterol, anti-HIV, antibacterial, antifungal, analgesic, antitubercular, and an and their pharmacological and biological activities [12]. Salama, Ahmed, and Hassan (2017) synthesized and characterized Co2+ complexes of amino acid Schiff bases from salicylaldehyde and three amino acids in basic medium and studied their biological activities[13].Iron-containingcomplexesareusefulinagriculture andotherbiologicalapplications.Arourietal.(2021)synthesized theFeCl4 (C5N2H6 )(C5N2H5 )complexandcharacterizeditbyX-ray, IR,UVmethodsand appliedit forvarioususes [14].Iyelabola,Akinkunmi,andAkinade(2020)synthesizedandcharacterizedmixed ligand complexes of Co+2, Ni+2 and Cu+2 with 1,10- phenantroline and (±)-2-amino-3-(4-hydroxyphenyl)propionic acid as ligands and reported their biological activities [15]. Moriguchi, Kawata, and Jalli (2021) synthesized a new hydrogen-bonded cobalt(II) complex and used the title complex for therapeutic applications [16]. Nenwa et al. (2014) isolated an aqueous solution at room temperatureandobtainedanoveltrinuclearheterothalliccomplex of Cr+2 [17]. Fomuta et al. 2017 synthesized and characterized a new Ag+2 complex [18]. Similarly, Moriguchi, Kawata, and Jalli 2021synthesizedfourneweuropiumcomplexesandreportedphotoelectronic property applications in light-emitting devices [16]. Zincisessentialtoallformsoflife[19];althoughCu-Ncomplexes arealsowellknownforcatalysingorganicreactions,ourresearch team successfully synthesized and characterized Cu+2, Zn+2 and Co+2 complexes. Additionally, our synthesizing method is novel due to its fruitfulness, low toxicity compared to other synthetic methods, lack of fume production, low cost and environmental friendliness.Consideringthesesignificantfactors,ourproductwill be beneficial for anticancer activities as well as other medicinal applications and industrial applications. Although our product is air-stable, it could potentially be used for medicinal uses or other human development applications. Inthispaper,wefirstdescribetheseveralnovelcomplexes, [CoC46H60Cl2N8O4 ](I),[CuC43H53Cl2N7O3 ](II),[CuC4H16Cl2N4O8 ] (III) and [Cl4 Zn, C13H28N2 , H2O] (IV), prepared with the one-pot methodshowninScheme1andpresenttheircrystalstructures obtained by single-crystal X-ray diffraction and characterization byvariousspectroscopictechniques.Additionally,ourcomplexes have shown good cytotoxicity to lung cancer cells but negligible toxicity towards normal cells. The synthesized complexes were also applied for the catalysis of some important organic reactions and obtained good results.

3. Experimental Scheme1: The synthetic route to complexes(I)-(IV) Chemical shiftsare reported inppm(δ) wit hthe solvent relative Materials and Methods 2,4-Di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol,ethane1,2-diamineCo(NO).6HO,Cu(ClO).6HOandZnClwere to tetramethylsilane (TMS), which was employed as the internal standard (residual CHCl3, δH 7.26 ppm; CDCl3, c 77 ppm). The followingabbreviationsareusedtodesignatemultiplicities:s= 32 2 42 2 2 singlet,d=doublet,t=triplet,m=multiplet.Infraredspectrawere purchasedfromAcros.1HNMRspectrawereobtainedusinga BrukerAM-300 spectrometer. 1H and 13C NMR spectra were recordedusingBrukerAM-500andBrukerAM-600spectrometers. recordedonaMattsonGalaxySeriesFTIR3000spectrometer;the peaksarereportedincm−1.Elementalanalyseswereperformed onanElementalAnalyserAE-3000.Thecrystalstructureswere determined by a Gemini SUltra diffractometer.

CytotoxicityAssay The human tumour cell line againstA549 (lung cancer) was used inthecytotoxicassay.ThesecelllineswereobtainedfromATCC (Manassas, VA, USA). Cells were cultured in RMPI-1640 or DMEM (Biological Industries, Kibbutz Beit Haemek, and Israel) supplemented with 10% foetal bovine serum (Biological Industries) at 37 °C in a humidified atmosphere with 5% CO2.The cytotoxicityassaywasevaluatedbyusingtheMTS(Promega,Mad- ison, WI, USA) assay. The cytotoxicity assay was evaluated by using the 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphe- nyl)- 2-(4-sulfophenyl)-2H-tetrazolium,innersalt(MTS)(Promega,Madison,WI,USA)assay.Briefly,cellswereseededintoeach wellofa96-wellcellcultureplate.After12hofincubationat37 °C,atestcompound(100μM)wasadded.Afterincubationfor48 h, the cells were subjected to the MTS assay. Compounds with a growth inhibition rate of 50% were further evaluated at concentrations of 0.064, 0.32, 1.6, 8, 40 and 100 μM in triplicate with cisplatin and paclitaxel (Sigma, St. Louis, MO, USA) as positive controls.

General Experimental Details found.Theselectionbetweentheavailablesolventssuchasanhydrousmethanol,ethanol, chloroform,etc. isthe mostcritical step. 3.4.1.SynthesisofComplex(I) Co(NO3 ) 2 .6H2O (0.290 g, 0.001 mmol) dissolved in methanol (10 ml) was added dropwise to a hot solution of the ligand (0.7200 g, 0.0020mmol)inmethanol(30ml).Themixturewasrefluxedwith heatfor24hr.Afterhotfiltration,thefiltratewasretainedfornaturalevaporationatroomtemperature.Aftertwodays,theproduct was dissolved in methanol, and a small amount of DMF and the filtrate held for natural evaporation. After three days, bright red crystals appeared in the solution. These were suitable for X-ray single-crystal analysis resulting in a 85% yield, m.p. 118-120 °C, IRpeaksat(KBr;ν,cm–1 )3397,2955,1651,1559,1478,1437, 1387,1360,1248,1202,1003,1048,937,845,834,805,752, 708,670,638,and587,1HNMRresultsof(600MHz,cdcl3)δ 8.02–7.99(s,1H),3.54–3.51(s,2H),3.49–3.46(s,3H),3.44–3.41 (s,4H),3.36–3.33(s,2H),2.99–2.96(s,2H),2.94–2.91(s,4H), 2.90–2.87(s,5H),2.85–2.82(s,5H),2.82–2.79(s,5H),2.75–2.72 (s, 3H), 2.63–2.60 (s, 1H), and 1.31–1.28 (s, 1H). SynthesisofComplex(II) Complex(II)wassynthesizedfollowingthegeneralprocedureusingmetalsaltCu(OAc).HO(0.180g,0.001mmol)dissolvedin 2 2 All reactions were performed in flame-dried glassware under normal atmospheric pressure. Reagents were obtained from commercial sources. Nuclear magnetic resonance (NMR) spectrawere acquired on a 500 MHz Bruker Advance III spectrometer. Infrared spectra were recorded on a Mattson Galaxy Series FTIR 3000spectrometer;peaksarereportedincm–1 .Elementalanalysis wasperformedonaVARIOELIIIelementalanalyser.Thecrystal structuresweredeterminedbyusingaGeminiSUltradiffractom- eter. 1H and 13C NMR chemical shifts are reported in ppm and referencedtoCDCl3,7.26ppm;forDMSO-d6,2.50ppm.Thefollowing abbreviations are used: s = singlet, d = doublet, t = triplet, q=quartet,m=multiplet.Meltingpointsweremeasuredbyusing aYanacoMicroMeltingPointSystemMP-J3andSANSYOMelt- ing Point Apparatus SMP-500 and are uncorrected.

GeneralProcedurefortheSynthesisofComplexes(I)-(IV) Ligand and metal salts (molar ratio of 2:1) were heated and refluxedfor48h,thenfiltrationwasconductedimmediatelyafterthe reaction, and the filtrate was retained for slow volatilization. The metal-ligand complexes were successfully synthesized by reacting2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol,ethane1,2-diamine and 4,4’-diaminocyclohexylmethane as ligands with Cu(ClO4)2 .6H2O, Co(NO3 ) 2 .6H2O and ZnCl2,respectively, andthe cultivated crystals were analysed and characterized by X-ray diffraction, IR, 1HNMR, 12CNMR, UV and E.A. The first key is to find the right ligands, and then the ligands and the corresponding metal salts were reacted. At the end of the reaction filtration wascarriedoutandasuitablesolventforcrystalprecipitationwas

3.4.1.SynthesisofComplex(I)Co(NO3 ) .6H2O (0.290 g, 0.001 mmol) dissolved in methanol (10 ml) was added dropwise to a hot solution of the ligand (0.7200 g, 0.0020mmol) inmethanol (30ml).The mixture was refluxed with heat for 24hr. After hot filtration, the filtrate was retained for naturalevaporationatroomtemperature.Aftertwodays,theproduct was dissolved in methanol, and a small amount of DMF and the filtrate held for natural evaporation. After three days, bright red crystals appeared in the solution. These were suitable for X-ray single-crystal analysis resulting in a 85% yield, m.p. 118-120 °C, IRpeaksat(KBr;ν,cm–1 )3397,2955,1651,1559,1478,1437, 1387,1360,1248,1202,1003,1048,937,845,834,805,752, 708,670,638,and587,1HNMRresultsof(600MHz,cdcl3)δ 8.02–7.99(s,1H),3.54–3.51(s,2H),3.49–3.46(s,3H),3.44–3.41 (s,4H),3.36–3.33(s,2H),2.99–2.96(s,2H),2.94–2.91(s,4H), 2.90–2.87(s,5H),2.85–2.82(s,5H),2.82–2.79(s,5H),2.75–2.72 (s, 3H), 2.63–2.60 (s, 1H), and 1.31–1.28 (s, 1H).

SynthesisofComplex (III) Similarly, complex (III) was also synthesized following the general procedure using ethanediamine (0.710 g, 16.10 mmol) as a ligandandCu(ClO4) 2 .6H2O(2.964g,8.00mmol)asthemetalsalt (2:1). The reaction mixture was refluxed with heat for two days, filtered while hot and retained for natural evaporation. After one day, blue crystals that appeared at the bottom of the beaker that were suitable for X-ray single-crystal analysis resulting in 80.2% yield, m.p. 280–285 °C. IR peaks at (KBr; ν, cm–1): 3337, 3281, 2988,1590,1467,1321,1280,1108,1066,1021,919,884,701, and 620.The calculated compositions in % for [C4H16Cl2CuN4O8 ] are: C, 12.56; H, 4.18; and N, 14.63 while the analysed compositions in % were: C, 12.98; H, 4.332; and N, 15.05. SynthesisofComplex(IV) For complex (IV), using the general procedure, ZnCl2 (1.14 g, 0.0052 mmol) metal salt was added dropwise to a hot solution of ligand (1.10 g, 0.00522 mmol) in methanol (30 ml).After hot filtration, the filtrate was retained for natural evaporation at room temperature.Aftertwodays,whitecrystalsappearedinthesolu- tion. These were suitable for X-ray single-crystal analysis resulting in 90% yield, m.p. 320 °C. IR peaks at (KBr; ν, cm–1): 3366, 3124,2925,2860,1597,1574,1387,1503,1485,1452,1386, 1248,1200,1054,1045,1122,1021,999,971,932,897,669, 657, 603, and 570.The 1H NMR results were (600 MHz, cdcl ) δ 12.56–12.52(s,23H),9.14–9.09(m,3H),7.95–7.92(s,1H),and 6.45–6.33 (m, 1H).

3.4.5. X-ray Structure X-raydiffractiondataforcomplexes(I)-(IV)werecollectedat roomtemperatureusinggraphite-monochromaticMoKαradiation (λ=0.71073Å)onanOxfordDiffractionGeminiSdiffractometer. Structure solutions and refinements for complexes 1-2 were carried out with the programs SHELXT [20] and SHELXL-2018/3 [21], respectively. MERCURY[22] was employed for molecular graphics and OLEX2 [23]. Nonhydrogen atoms in (I)-(IV) were refined anisotropically, while hydrogen atoms were treated by constrained isotropic refinement. Crystal data and refinement parameters for complexes (I)-(IV) are summarized in Table 1. The selectedbondlengthsandbondanglesareshowninTableS1,and hydrogen bonds of complexes I-IV are listed in Table 2.

4. ResultsandDiscussion SynthesisMethod Complexes (I)-(IV) were synthesized using the one-pot synthetic method. The synthetic route can be seen in Scheme 1. (1): The syntheses of complexes (I)-(IV) were carried out under anhydrousmethanol/ethanolusing4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl) phenol, ethane-1,2-diamine, and 2,4’-diaminocyclohexylmethane as ligands with different metal salts, i.e., Co(NO3) 2 .6H2OandCu(OAc)2 .H2O,Cu(ClO4 ) 2 .6H2OandZnCl2, respectively(2:1eq).The mixtureswererefluxedfor48h.After hotfiltration,crystalswereobtainedwhenthesolutionwasevaporatedslowlyintheair.Thecrystalswereconfirmedandcharacterizedbydifferentspectroscopictechniques,suchasUV,IR,andE. A,ES-MSI aswell asXRD.

CrystalStructureAnalysis (1):Thecrystalsizeofcomplex(I)is0.15x0.1x0.1mm3.They havereddishcolourand,belongtothemonocliniccrystalsystem. AccordingtotheX-raydataoffourroundsinglecrystals,themolecularweightofthiscrystalis918.85,andthespacegroupisP1 21/c 1. The cell parameters are a = 14.6703(6) Å, b = 18.5175(8) Å,c=18.5323(8)Åandα=90°,β=105.7200(10)°,γ=90°,V= 4846.1(4)Å3,Z=4,D=1.259Mg/m3,andF(000)=1940.The bondlengthsandanglesforcomplexIIare[(Co1)-(N1) 2.1460(13) Å],[(Co1)-(N4)2.1816(14)Å],[(Co1)-(O1)1.9730(12)Å], [(Co1)-(O2) 1.9642(12) Å], [(Co1)-(O3) 2.1888(14) Å], and [(Co1)-(O4) 2.1792(13) Å]. (2):Complex(II)wascrystallizedundercertainexperimentalconditions, i.e., P-1 shown in Table 1. For mono-nuclearmetalcomplex(I),thereisonemetalionandtwoligandspresentaswellasa DMF solvent molecule in the crystal structure. The bluish crystals of complex (II) are composed of the central Cu ion and they adopt square-planar coordination by two ligands andoneDMFsolventmolecule.ThefivebondlengthsaredCu1-O1 =1.9055(15)Å,dCu1-O2=1.9115(15)Å,dCu1-N1=2.0446(18)Å, dCu1-N4 = 2.0686(18) Å and dCu1-O3= 2.1954(19). The angles around the Cu centre are [O(1)-Cu(1)-O(2) 178.96(6)], [O(1)-Cu(1)-N(1) 88.16(7)], [O(2)-Cu(1)-N(1) 91.05(7)], [O(1)-Cu(1)-N(4) 92.94(7)], [O(2)-Cu(1)-N(4) 88.10(7)], [N(1)-Cu(1)-N(4) 130.45(7)], [O(1)-Cu(1)-O(3) 90.64(7)], [O(2)-Cu(1)-O(3) 89.19(7)],[N(1)-Cu(1)-O(3)122.01(8)]and[N(4)-Cu(1)-O(3) 107.51(8)]. Thecrystalsizeofthecomplexis0.130x0.100x0.080mm3 ,belonging to the monoclinic crystal system.According to the X-ray data of four round single crystals, the molecular weight of this crystal is 850.36, and the space group is P-1. The cell parame-ters are a = 104.587(6)° Å, b = 13.777(2) Å, c = 14.999(2) Å, α= 104.587(6)°,β=99.918(5)°,andγ=96.032(5)°.V=2129.2(6)Å3, D=1.326Mg/m3andZ=2.Thebondlengthsandanglesforcomplex(I)are:[(Cu1)-(O1)1.9055(15)Å],[(Cu1)-(O2)1.9115(15) Å],[(Cu1)-(O3)2.1954(19)Å],[(Cu1)-(N1)2.0446(18)Å]and [(Cu)-(N4)]2.0686(18)Å]and[O(1)-Cu(1)-O(2)]178.96(6), [O(1)-Cu(1)-N(1)]88.16(7),[O(2)-Cu(1)-N(1)]91.05(7),[O(1)- Cu(1)-N(4)] 92.94(7), [O(2)-Cu(1)-N(4)] 88.10(7), [N(1)- Cu(1)-N(4)]130.45(7),[O(1)-Cu(1)-O(3)]90.64(7),[O(2)- Cu(1)-O(3)]89.19(7),[N(1)-Cu(1)-O(3)]122.01(8)and[N(4)- Cu(1)-O(3)]107.51(8).Selectedbondlengths(Å)andangles(°) areshowninTableS2.Hydrogenbondsforthecomplexes[Åand °]areshownin(Table2). (3):Thecrystalsofcomplex(III)haveabluecolour.Accordingto the X-ray data of four round single crystals, the molecular weight ofthiscrystalis382.65,thesizeis0.12x0.1x0.1mm3,thecrystalsystemistriclinic,andthespacegroupisP-1.Thecellparam- eters are: a = 5.7113(18) Å, b= 7.804(2) Å c = 7.963(3) Å and α= 75.313(4)°.β=79.154(5)°.andγ=77.952(4). V=332.31(18)Å3, Z=1, D=1.912 Mg/m3, andF (000)=195.Allbond lengths and anglesforcomplex(III)are[(Cu1)-(N1)2.018(2)Å],[(Cu1)-(N1) 2.018(2) Å], [(Cu1)-(N2) 2.015(2) Å], and [(Cu1)-(N2) 2.015(2) Å]. (4): The crystal size of complex (IV) is 0.22 x 0.1 x 0.1 mm3, their colour is white, and they belong to the monoclinic crystal system.AccordingtotheX-raydataoffourroundsinglecrystals, themolecularweightofthiscrystalis437.56,andthespacegroup is P 1 21/c 1. The cell parameters are: a = 7.57262(12) Å, b = 10.62573(18)Å,c=25.0728(5)Å,α=90°,β=96.2309(16)°,γ= 90°,V=2005.55(6)Å3,Z=4,Dcalc=0.3351.259Mg/m3,andF (000) = 912. The bond lengths and angles for complex (IV) are [(Zn1)-(Cl2)2.2739(6)Å],[(Zn1)-(Cl4)2.2648(6)Å],[(Zn1)- (Cl3)2.2563(6)Å],[(Zn1)-(Cl1)2.2889(6)Å],[(Cl2)-(Zn1)-(Cl1) 110.38(3)Å],[(Cl4)-(Zn1)-(Cl2)106.87(2)Å],[(Cl4)-(Zn1)–(Cl1) 111.52(3)Å],[(Cl3)-(Zn1)-(Cl2)110.25(2)Å],[(Cl3)-(Zn1)-(Cl4) 110.69(3)Å],and[(Cl3)-(Zn1)-Cl1)107.17(2)Å].

IRspectroscopyofcomplexes(I)-(IV) The IR analyses show several peaks that can be found in all IR spectra (shown in Fig. 1).These include all C-H stretching vibrations between 3000 and 2800 cm−1, C=C stretching vibrations at approximately11600cm−1,andC-Ovibrationsat1280/1090cm−1 [24]. The 3100 to 3000 cm−1 peak of the aromatic C-H stretching vibration combines stronger absorption at 1600 cm−1 , , which can be referred to as aromatic C-C double bonds, and aliphatic C-H stretching vibrations in the range between 3000 and 2800 cm−1 . The determination of aromatic structures has been supported by the presence of the spectral region between 1500-1630 cm−1; the absorbancebandsat1300cm−1to1400cm−1canbeassignedtothe bending vibrations of the CH3 group, and broad absorption in the regionbetween1050and1150cm−1isdominatedbyC-Ostretch- ing vibrations [25]. Stretching vibration peaks appeared at 600- 650 cm-1 and 500-600 cm-1 for metal-nitrogen and metal-oxygen bonds,respectively,andapeakappearedat650-700cm-1 forC-Cl. UV-visiblespectroscopyforcomplexesI-IV The absorption spectra of the complexes and raw materials were recorded in methanol. The broad peaks at 230 nm, 250 nm, 311- 344nmand359nmareduetoσ-σ*andn-σ*,π-π*andn-π*transitions[21, 22,23, 24].TheUVspectraofthecomplexesarepresented in Figure 2.

CytotoxicityAssay Figure2.UV‒visiblespectraofcomplexes(I)-(IV) 4.0,20and100μMintriplicatewithcisplatinandpaclitaxel (SigThe human tumour cell line SMMC-7721(Liver cancer)wasusedinthecytotoxicassays.Thesecelllineswereobtainedf rom ATCC(Manassas,VA,USA).CellswereculturedinRMPI-1640 or DMEM (Biological Industries, Kibbutz Beit Haemek, Israel) supplemented with 10% foetal bovine serum, (Biological Industries) at 37 °C in a humidifiedatmosphere with 5% CO2.The cytotoxicityassayswereevaluatedbytheMTS(Promega,Madison, WI, USA) assay method. The cytotoxicity assays were evaluated bythe3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)- 2-(4-sulfophenyl)-2H-tetrazolium, inner salt (MTS) (Promega, Madison,WI,USA)assaymethod[12].Briefly,cellswereseeded intothewellsofa96-wellcellcultureplate.After12hofincuba- tion at 37 °C, the 100 μM of the appropriate test compound was added to each well.After incubation for 48 h, the cells were subjectedtotheMTSassay.Compoundswithagrowthinhibitionrate of50%,orhigher,werefurtherevaluatedatamountsoff0.16,0.8, ma,St.Louis,MO,USA)aspositivecontrols.TheIC50valuesof eachcompoundwerecalculatedwithReedandMuench’smethod [13]. The results are presented in Table 3. By comparing the activity of complexes (I)–(IV), complex (II) showedthebestcytotoxiceffectsagainstthelungcancercellLine A549,withanIC50valueof19.92µM.Cisplatinisalsoshownfor the sake of comparison, as shown Table 3.

4.6 Catalytic application Catalysis of Henryreaction, showninscheme2, wasachievedusing 10mmol% complexes (I)to(IV) with out any additives. Using complexes (I) to (IV) (0.10 mmol), benzaldehyde (0.10 mL), and nitromethane (0.50mL) weresuccessivelyaddedtogetherin2mL anhydrous methanol at room temperature for 24 h [30-38]. The catalytic activities of the novel complexes in the Henry reactionarepresentedinTable4.Thistableshowsthattheconversion efficiencyofthesethreeofthecomplexeswasmorethan85%,and thattheyaregoodcatalystsfortheHenryreaction.Themechanism that can be proposed is that the complexes could greatly activate theC=Obond,andthenthereisanucleophilicadditionreactionof CH NO -onto the carbonyl group:

5. Conclusions Scheme2.Henry reaction In addition to describing their synthesis, and characterization this paper also presents the anticancer and catalytic activities of mononuclearCu2+,Co2+andZn2+complexesinvolving2,4-di-tert-bu- tyl6-(5-chlorobenzotriazol-2-yl) phenol and ethane-1,2-diamine ligands and 2,4’-diaminocyclohexylmethane ligands. The synthesizedcomplexeswereconfirmedandcharacterizedusingtechniques such as FTIR, NMR, UV–visible and E. A, as well as by single-crystal X-ray diffraction. Our synthesized complexes can be used in medicinal as well catalytic applications. Additionally, they showed cytotoxic activity against A549 cells. Among them, complex (II) exhibited the best bioactivity against A549 cells compared to other complexes, with an IC50 value of 19.92 μM. Theresultsclearlyshowthattheanticanceractivityofthesecomplexes depends on the type of metal ion and cell line, as well as the geometries of the corresponding compounds.These useful results provide motivation for the design and development of new therapeuticdrug-likemolecules.Thesynthesizedcomplexeswere tested in some catalytic reactions obtaining excellent results.

6. Acknowledgements This work was supported by the Hefei University of Technology andStateKeyLaboratoryofPhotochemistryandPlantResources in West China.

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