New Structural Topologies in a Series of 3d Metal Complexes withIsomeric Phenylenediacetates and 1,3,5-Tris(1-imidazolyl)benzeneLigand: Syntheses, Structures, and Magnetic and LuminescencePropertiesSandip Mukherjee, Dipak Samanta, and Partha Sarathi Mukherjee*

Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India

*S Supporting Information

ABSTRACT: In this article we present the syntheses, char-acterizations, magnetic and luminescence properties of five3d-metal complexes, [Co(tib)(1,2-phda)]n·(H2O)n (1),[Co3(tib)2(1,3-phda)3(H2O)]n·(H2O)2n (2), [Co5(tib)3(1,4-phda)5(H2O)3]n·(H2O)7n (3), [Zn3(tib)2(1,3-phda)3]n·(H2O)4n (4), and [Mn(tib)2(H2O)2]n·(1,4-phdaH)2n·(H2O)4n(5), obtained from the use of isomeric phenylenediacetates(phda) and the neutral 1,3,5-tris(1-imidazolyl)benzene (tib)ligand. Single crystal X-ray structures showed that 1 constitutes3,5-connected 2-nodal nets with a double-layered two-dimen-sional (2D) structure, while 2 forms an interpenetrated 2Dnetwork (3,4-connected 3-nodal net). Complex 3 has a com-plicated three-dimensional structure with 10-nodal 3,4,5-connected nets. Complex 4, although it resembles 2 in stoichi-ometry and basic building structures, forms a very different overall 2D assembly. In complex 5 the dicarboxylic acid, upon losingonly one of the acidic protons, does not take part in coordination; instead it forms a complicated hydrogen bonding network withwater molecules. Magnetic susceptibility measurements over a wide range of temperatures revealed that the metal ions exchangevery poorly through the tib ligand, but for the Co(II) complexes the effects of nonquenched orbital contributions are prominent.The 3d10 metal complex 4 showed strong luminescence with λmax = 415 nm (for λex = 360 nm).

■ INTRODUCTION

The search for new structural topologies in the field of metal−organic-frameworks (MOFs) and coordination polymers (CPs)has accelerated over the last two decades.1 Many of thesematerials were also found to be suitable for uses in catalysis,2

gas-adsorption/separation,3 luminescence,4 magnetism,5 ionexchange,6 electrical applications,7 and synthesis of nanoma-terials.8 There are two main approaches to build multidimen-sional metal-coordination based structures. The first approachof predesign is attractive because of the possible control of theresulting topologies.1 However, the other route to such systemstakes advantage of the versatility of several bridging ligands(carboxylato, azido, etc.). These so-called “serendipitousassemblies” continue to provide topologies that are otherwisedifficult to design.9

There is however a third solution to the same problem thatcan take advantage of both of the above approaches. In a three-(or more) component assembly of a metal ion and two differentligands, if one of the ligands is flexible in nature with a range ofpossible conformations, the resulting framework can still benovel in topology, although parts of it may be restricted bygeometry of the rigid ligand component.10 The benzenedicar-boxylates have been widely used in MOFs as rigid anionic

linkers.11 However, the three isomeric phenylenediacetates canbehave as flexible dianionic bridges.12 The pyridine based ligandsare generally preferred as rigid neutral bridging ligands (althoughthe backbone of these ligands can be modified to make themflexible).13 The imidazole-based bridging ligands with similarbackbones have a more interesting coordination behavior.14

For this reason, 1,3,5-tris(1-imidazolyl)benzene (tib) is wellrepresented in MOFs and also in coordination-driven self-assembled structures.15,16

We were interested to see the results of the combination ofthe flexible phenylenediacetates and the semirigid tib ligandwith 3d metal ions. With their intricate structural possibilities,the use of paramagnetic metals may produce interesting mag-netic properties as well. Therefore, herein we report the syntheses,structures, magnetic and luminescence property studies of five3d-metal complexes [Co(tib)(1,2-phda)]n·(H2O)n (1),[Co3(tib)2(1,3-phda)3(H2O)]n·(H2O)2n (2), [Co5(tib)3(1,4-phda)5(H2O)3]n·(H2O)7n (3), [Zn3(tib)2(1,3-phda)3]n·(H2O)4n(4), and [Mn(tib)2(H2O)2]n·(1,4-phdaH)2n·(H2O)4n (5), obtained

Received: August 6, 2013Revised: October 29, 2013

Article

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from the use of isomeric phenylenediacetates (phda) and thetib ligand. Single crystal X-ray structures showed that 1, 2, and4 constitute novel net structures with overall two-dimensional(2D) arrangements. The three-dimensional (3D) structure ofcomplex 3 is featured by 10-nodal 3,4,5-connected nets. Incomplex 5 the monoanionic 1,4-phdaH moieties form acomplicated hydrogen bonding network with water molecules,while the tib ligand forms a four connected coordinationnetwork working as a bidentate ligand.

■ EXPERIMENTAL SECTIONMaterials. 1,3,5-Tris(1-imidazolyl)benzene (tib) was prepared as

described in the literature.15n All the other chemicals were obtainedfrom commercial sources and were used without further purification.Physical Measurements. Elemental analyses of C, H, and N were

performed using a Perkin-Elmer 240C elemental analyzer. IR spectrawere recorded as KBr pellets using a Magna 750 FT-IRspectrophotometer. The phase purity of the as-synthesized complexeswas verified by powder XRD data collected using a D8 Advance X-raydiffractometer (Figure S1, Supporting Information). The measure-ments of variable-temperature magnetic susceptibility were carried outon a Quantum Design MPMS-XL5 SQUID magnetometer. Suscept-ibility data were collected using an external magnetic field of 0.1 Tfor all the complexes in the temperature range of 2−300 K. Theexperimental susceptibility data were corrected for diamagnetism(using Pascal’s tables).17

Synthesis of the Complex [Co(tib)(1,2-phda)]n·(H2O)n (1). Co-(OAc)2·4H2O (50 mg, 0.2 mmol), 1,2-phdaH2 (39 mg, 0.2 mmol),and tib (55 mg, 0.2 mmol) were taken in 12 mL of water, and theresulting mixture was stirred for 15 min at room temperature. Thereaction mixture was then transferred to a 23 mL Teflon-linedhydrothermal flask and was heated at 130 °C for 60 h. Slow cooling ofthe mixture down to room temperature (in 24 h) gave rectangular pinkcrystals which were washed with methanol and dried. Isolated yield:∼69% based on available Co(II). Anal. Calcd for 1, C25H22N6O5Co: C,55.05; H, 4.07; N, 15.41. Found: C, 55.00; H, 4.31; N, 15.18. IR (KBr,cm−1): 3121(w), 2177(w), 1596(s), 1552(s), 1503(s), 1403(m),1347(s), 1251(m), 1072(m), 751(m), 651(m).Synthesis of the Complex [Co3(tib)2(1,3-phda)3(H2O)]n·(H2O)2n

(2). This complex was isolated as rectangular dark-pink crystals underidentical conditions as for complex 1 using 1,3-phdaH2 (39 mg,0.2 mmol). Isolated yield: ∼64% based on available Co(II). Anal.Calcd for 2, C60H54N12O15Co3: C, 52.99; H, 4.00; N, 12.36. Found: C,53.31; H, 4.23; N, 12.59. IR (KBr, cm−1): 3119(w), 2141(w),2172(w), 1621(m), 1558(s), 1509(m), 1384(m), 1278(m), 1073(m),750(m), 648(m).Synthesis of the Complex [Co5(tib)3(1,4-phda)5(H2O)3]n·(H2O)7n

(3). Co(OAc)2·4H2O (50 mg, 0.2 mmol), 1,4-phdaH2 (39 mg,0.2 mmol), and tib (55 mg, 0.2 mmol) were taken in 12 mL of water,and the resulting mixture was stirred for 15 min at room temperature.The reaction mixture was then transferred to a 23 mL Teflon-linedhydrothermal flask and was heated at 150 °C for 60 h. Slow coolingof the mixture down to room temperature (in 24 h) gave rectangulardark pink crystals which were washed with methanol and dried.Isolated yield: ∼74% based on available Co(II). Anal. Calcd for 3,C95H96N18O30Co5: C, 50.39; H, 4.27; N, 11.13. Found: C, 50.31; H,4.38; N, 11.22. IR (KBr, cm−1): 3129(w), 2136(w), 2022(w), 1533(s),1503(s), 1400(s), 1240(m), 1071(m), 851(m), 712(m), 649(m).Synthesis of the Complex [Zn3(tib)2(1,3-phda)3]n·(H2O)4n (4). The

colorless rectangular shaped crystals of 4 were obtained by a methodsimilar to that described above, using Zn(NO3)2·6H2O (60 mg,0.2 mmol) and 1,3-phdaH2 (39 mg, 0.2 mmol). Isolated yield: ∼65%based on available Zn(II). Anal. Calcd for 4, C60H56N12O16Zn3: C,51.57; H, 4.04; N, 12.03. Found: C, 51.32; H, 3.79; N, 12.29. IR (KBr,cm−1): 3131(w), 2203(w), 2037(w), 1593(s), 1582(s), 1510(s),1367(s), 1073(m), 845(m), 718(m), 650(m).Synthesis of the Complex [Mn(tib)2(H2O)2]n·(1,4-phdaH)2n·

(H2O)4n (5). The rectangular-shaped colorless crystals of 5 were alsoobtained by a similar method, using Mn(OAc)2·4H2O (49 mg,

0.2 mmol) and 1,4-phdaH2 (39 mg, 0.2 mmol). Isolated yield: ∼30%based on available Mn(II), ∼60% based on the other two components.Anal. Calcd for 5, C50H54N12O14Mn: C, 54.50; H, 4.94; N, 15.25.Found: C, 54.34; H, 4.88; N, 15.11. IR (KBr, cm−1): 3720(w),3675(w), 3131(w), 2199(w), 2165(w), 2041(w), 1620(m), 1499(w),1232(w), 1075(s), 1080(s), 831(m), 739(m), 611(m).

X-ray Crystallographic Data Collection and Refinements.Single crystal X-ray data for all the five complexes were collected on aBruker SMART APEX CCD diffractometer using the SMART/SAINTsoftware.18 Intensity data were collected using graphite-monochrom-atized Mo Kα radiation (0.71073 Å) at 293 K. The structures weresolved by direct methods using the SHELX-9719 program incorporatedinto WinGX.20 Empirical absorption corrections were applied withSADABS.21 All non-hydrogen atoms were refined with anisotropicdisplacement coefficients. The hydrogen atoms bonded to carbon wereincluded in geometric positions and given thermal parametersequivalent to 1.2 times those of the atom to which they wereattached. Hydrogen atoms on some of the free and coordinated watermolecules could not be found. The value of Rint for 3 is higher than0.12, but the reported structure has the best value (0.165) amongseveral attempts that we made for the X-ray data collection for thiscomplex. Crystallographic data and refinement parameters are given inTable 1, and important interatomic distances and angles are given inTable S1, Supporting Information.

■ RESULTS AND DISCUSSION

Synthesis. All the five complexes were obtained from thehydrothermal reactions with equimolar quantities of thedivalent metal salt, the phenylenediacetates and the tib ligandunder identical conditions. We carried out these reactions withthe three possible dicarboxylates for metal nitrate and acetatesalts of cobalt, zinc, and manganese. However, for cobalt onlythe reactions with the acetate salt produced crystalline com-pounds under the given conditions. For zinc and manganese,only one combination of each of the components producedcrystalline products under identical hydrothermal conditions.However, in a recent report Sun et al. reported a Zn(II)complex with 1,2-phda and tib ligand, although the syntheticmethod used was different.15p

The parallel experiments prove that the quality of crystalsand the yields were optimal at the reported conditions. Com-plex 3 can also be obtained in high yields at 130 and 140 °C,but the crystalline material obtained at 150 °C was found to bethe purest form of the complex. The resultant complexes,obtained as crystalline solids, are easy to isolate and are stablein air and insoluble in water or in common organic solvents.The manganese complex is unique as the dicarboxylic acid

only acts as a monoanionic counterion for the Mn−tib frame-work and does not take part in coordination. It is also interest-ing to note that although we used the same initial molar ratiosfor the components, the three different dicarboxylates producedcomplexes with different metal to tib ratios. The 1,3-phda com-plexes for both cobalt and zinc have the same ratios of thesecomponents, although they have different overall structures(both 2D). All the products formed with high yields, and theirbulk purity was confirmed through powder XRD measurementsof the as-synthesized complexes (Figure S1, Supporting Informa-tion) and was found to closely match with the simulatedspectra. The sharp and strong IR peaks in the 1300−1600 cm−1

range could be attributed to the carboxylate groups.Structure Description of [Co(tib)(1,2-phda)]n·(H2O)n (1).

This complex crystallizes in the monoclinic space group P21/nrevealing a 2D double-layered arrangement, consisting of twolayers of Co−tib framework linked by 1,2-phda bridges. Theasymmetric unit consists of one metal atoms, one tib ligand,

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one dianionic 1,2-phda ligand, and one free water molecule.The Co(II) ions have distorted octahedral geometry (Figure 1),with the equatorial sites occupied by two oxygen atoms ofa chelating carboxylate group [Co(1)−O(1), 2.256(2) Å;Co(1)−O(2), 2.204(2) Å], one oxygen atom from the othercarboxylate group [Co(1)−O(3)#1, 2.054(2) Å] from adifferent 1,2-phda ligand (symmetry generated) and a nitrogenatom from a tib ligand [Co(1)−N(3)#2, 2.146(2) Å]. The twoaxial sites are taken up by two remaining nitrogen atoms fromdifferent symmetry generated tib ligands [Co(1)−N(1),2.090(2) Å; Co(1)−N(5)#3, 2.115(2) Å with the angle ∠N(1)−Co(1)−N(5)#3, 171.00(8)°]. The tib ligand acting as a three-connected node joins the Co(II) ions to form a 2D extendedstructure, in which the metal ions are also three connected(Figure 2a). Two of these adjacent layers are joined togetherby 1,2-phda bridges to form a double-layered 2D structure(Figure 2b,c). Overall, the metal atoms act as five connectednodes. The simplified 2D net structure of 1 reveals a new topology(to the best of our knowledge) and can be described in the

topological representation as 3,5-connected 2-nodal net with pointsymbol of {4.62}{43.67} (Figure S2, Supporting Information).

Structure Description of [Co3(tib)2(1,3-phda)3(H2O)]n·(H2O)2n (2). 2 crystallizes in the triclinic space group P1 andthe single crystal structure shows that it contains inter-penetrated 2D layered structure. The asymmetric unit consistsof three metal atoms [Co(1) is five-coordinated with a dis-torted square pyramidal geometry; Co(2) is four coordinatedwith slightly distorted tetrahedral geometry and Co(3) is sixcoordinated with highly puckered octahedral geometry], twotib ligands, three dianionic 1,3-phda ligands, and one co-ordinated and two free water molecules (Figure 3). Co(1) hasthree carboxylate oxygen (from two different 1,3-phda ligands)atoms [Co(1)−Ocrbx, 2.010(5), 2.019(4), 2.321(4) Å] and twoimidazole nitrogen atoms from two different tib ligands in itscoordination sphere [Co(1)−N(1), 2.074(5) Å; Co(1)−N(7),2.055(5)Å]. Co(2) has two carboxylate oxygen atoms and twoimidazole nitrogen atoms (all from different ligands) in itstetrahedral coordination sphere [Co(2)−O(3), 1.989(5) Å;Co(2)−O(9)#5, 1.947(5)Å; Co(2)−N(3), 2.045(5) Å; Co(2)−N(9)#6, 2.025(4) Å]. The equatorial sites of the roughly octa-hedral Co(3) atom are occupied by two oxygen atoms from thesame carboxylate group [Co(3)−O(11), 2.187(4) Å; Co(3)−O(12), 2.182(4) Å], one imidazole nitrogen atom [Co(3)−N(11)#7, 2.088(5) Å] and a coordinated water molecule[Co(3)-O(1W), 2.042(4) Å]. The axial positions are taken upby one carboxylato oxygen atom [Co(3)−O(7), 2.109(4) Å]and another imidazole nitrogen atom [Co(3)−N(5), 2.150(5) Å],with the angle between the two bonds as 177.2(2)°. The threeCo(II) ions and the two tib ligands form a one-dimensional(1D) layered arrangement running parallel to the crystallo-graphic b axis. In this arrangement the Co(1) and Co(2) atomsare linked by a 1,3-phda bridge, and the Co(2) and Co(3)atoms are linked by another 1,3-phda bridge. These chains arejoined to neighboring chains through 1,3-phda bridges joining

Figure 1. Thermal ellipsoid probability plot of the basic unit of 1.Hydrogen atoms and solvent water molecules have been removed forclarity. Thermal ellipsoids are at 30% probability level.

Table 1. Crystallographic Data and Refinement Parameters for 1−5

1 2 3 4 5

empirical formula C25H22N6O5Co C60H54N12O15Co3 C95H96N18O30Co5 C60H56N12O16Zn3 C50H54N12O14Mnfw 545.41 1359.94 2264.55 1397.33 1101.97T (K) 293(2) 293(2) 293(2) 293(2) 293(2)crystal system monoclinic triclinic monoclinic monoclinic monoclinicspace group P21/n P1 P21/n P21/c P21/na/Å 12.8344(4) 8.1702(4) 17.2061(8) 21.534(2) 8.5478(4)b/Å 10.3729(4) 15.7344(13) 16.2099(7) 13.1110(14) 18.0515(7)c/Å 17.5387(6) 22.5501(15) 34.9123(16) 21.387(2) 16.6294(6)α/deg 90.00 91.459(6) 90.00 90.00 90.00β/deg 93.849(2) 93.380(5) 94.604(3) 97.236(5) 98.933(2)γ/deg 90.00 93.366(5) 90.00 90.00 90.00V/Å3 2329.66(14) 2887.6(3) 9705.9(8) 5990.1(11) 2534.80(18)Z 4 2 4 4 2ρcalcd (g cm−3) 1.549 1.559 1.536 1.547 1.444μ (Mo Kα) (mm−1) 0.788 0.933 0.928 1.273 0.341λ/Å 0.71073 0.71073 0.71073 0.71073 0.71073F (000) 1116 1390 4588 2864 1150collected reflns 49037 27299 199398 81068 54089unique reflns 7148 13331 19867 11180 7741GOF (F2) 1.016 0.969 0.982 1.054 1.024R1a 0.0447 0.0775 0.0789 0.0423 0.0489

wR2b 0.1211 0.1597 0.1655 0.1117 0.1212

aR1 = Σ||Fo| − |Fc||/ Σ|Fo|. bwR2 = [Σ{w(Fo2 − Fc2)2}/Σ{w(Fo2)2}]1/2.

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the Co(1) and Co(3) atoms in the adjacent units to form a 2Darrangement. Two such 2D nets are interpenetrated with eachother and form the layered structure parallel to the crystallo-graphic ab plane and are stacked along the c axis (Figure 4).The topological analysis of the structure showed that the

complex consists of 3,4-connected 3-nodal nets with stoichio-metry (3-c)2(4-c)3, and the point symbol (Schlafli) for the netis {3.6.7}2{3.6

2.72.9}2{32.63.7}, which represents a new top-

ology (Figure S3, Supporting Information).Structure Description of [Co5(tib)3(1,4-phda)5(H2O)3]n·

(H2O)7n (3). This complex has a complicated 3D structure. Itcrystallizes in the monoclinic space group P21/n, and the asym-metric unit consists of five cobalt atoms, three tib ligands, five1,4-phda ligands, and three coordinated and seven free watermolecules (Figure 5). All the five metal ions have distortedoctahedral geometries. Co(1) has two pairs of chelatingcarboxylato oxygen atoms, a singly coordinated carboxylato oxy-gen atom [Co(1)−Ocrbx, 2.009(4)−2.262(4) Å] and an imidazolenitrogen atom [Co(1)−N(1), 2.050(5) Å] in its coordination

sphere. Co(2) has one pair of chelating carboxylato oxygenatoms, two singly coordinated carboxylato oxygen atom[Co(2)−Ocrbx, 2.017(4), 2.166(4) and 2.179(4) Å] and twoimidazole nitrogen atoms [Co(2)−Nim, 2.065(5) and 2.145(5) Å]in its coordination sphere. The six coordination sites of Co(3)are occupied by one pair of chelating carboxylato oxygen atoms,one singly coordinated carboxylato oxygen atom [Co(3)−Ocrbx,2.004(5), 2.111(5), and 2.366(5) Å] and three imidazole nitro-gen atoms [Co(3)−Nim, 2.095(5), 2.126(5) and 2.159(5) Å].Co(4) has one pair of chelating carboxylato oxygen atoms,one singly coordinated carboxylato oxygen atom, one watermolecule [Co(4)−O(1W), 2.111(5) Å] and two imidazolenitrogen atoms [Co(4)−Nim, 2.089(5) and 2.099(6) Å] in itscoordination sphere. The coordination sphere of Co(5) con-sists of one pair of chelating carboxylato oxygen atoms, one singlycoordinated carboxylato oxygen atom [Co(5)−Ocrbx, 2.040(4),2.153(5) and 2.190(5) Å], two water molecules [Co(5)−Owt,2.054(5) and 2.164(5) Å], and an imidazole nitrogen atom[Co(5)−N(11), 2.133(5) Å].The overall 3D structure of the complex is quite complicated,

so we have shown partial linkages of the carboxylato and tibbridges separately in Figure 6. Adjacent Co(1) and Co(2)atoms are bridged by a μ1,3-carboxylato [O(5)−C(18)−O(6)]and a μ1,1-carboxylato [O(2)] groups [Co(1)···Co(2), 3.913(1) Å,the angle ∠Co(1)−O(2)−Co(2), 121.2(2)°], a feature that isnot observed in the other complexes. The neighboring Co(2)and Co(3) atoms are joined by the distal carboxylato oxygenatoms of a 1,4-phda ligand and the two imidazole moieties of atib ligand at a distance of 10.141(1) Å. Again the neighboringCo(3) and Co(4) atoms are joined by the distal carboxylatooxygen atoms of a 1,4-phda ligand and two pairs of imidazolemoieties of two tib ligands at a distance of 9.530(1) Å. Co(5)is linked to Co(2) and Co(3) atoms through a tib bridge[Co(5)···Co(2), 12.436(1) Å; Co(5)···Co(3), 12.680(1) Å].The 1,4-phda ligand joining the Co(1) and Co(2) atoms byμ1,3-bridging also joins to the Co(5) atom through the othercarboxylato group (Figure 5).The network analysis reveals a new topology (Figure S4,

Supporting Information) with 3,4,5-connected 10-nodal netwith stoichiometry (3-c)3(4-c)(5-c) and the point (Schlafli)

Figure 2. (a) The 2D arrangement obtained by the linking of metal atoms by the tib ligands in 1. (b, c) Views of the double-layered 2D structure of1. The tib ligands in adjacent layers have been shown in different colors (dark yellow and sky blue). The 1,2-phda ligands joining the layers havebeen shown in magenta. Hydrogen atoms and free water molecules have been removed for clarity.

Figure 3. Thermal ellipsoid probability plot of the basic unit of 2.Hydrogen atoms and free solvent molecules have been removed forclarity. Thermal ellipsoids are at the 30% probability level.

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symbol as {103}{3 × 102}3{3.4 × 106.132}{32.4 × 102.11}{33.4 × 102.114}{4 × 102}2{4 × 104.13}.

Structure Description of [Zn3(tib)2(1,3-phda)3]n·(H2O)4n (4).This complex crystallizes in the monoclinic space group P21/cand has an overall 2D structure. Although the basic structure ofthis complex is remarkably similar to that of complex 2, theydiffer in their overall 2D arrangement. Three metal atoms [allhaving tetrahedral geometries], two tib ligands, three dianionic1,3-phda ligands, and four noncoordinated water moleculesconstitute the asymmetric structure (Figure 7) of 4. All themetal atoms have two carboxylato oxygen atoms [Zn−Ocrbx,1.920(4)−1.970(4) Å] and two imidazole nitrogen atoms [Zn−Nim, 1.972(4)−2.043(3) Å] in their coordination spheres. Themetal atoms, two tib ligands, and two 1,3-phda linkers con-stitute (similar to 2) a 1D arrangement running parallel to thecrystallographic c axis. Such 1D chains are joined to neighbor-ing chains through the bridging of the third dicarboxylateforming a 2D arrangement of the components parallel to the acplane (Figure 8). The topological analysis showed (Figure S5,Supporting Information) that the overall structure consists of3,4-connected 3-nodal nets with stoichiometry (3-c)2(4-c)3 andthe point symbol (Schlafli) for the net as {3.62}2{3.6

3.72}2-{32.62.72}, again representing a new topology among the MOFs.

Figure 4. (a) The 1D arrangement obtained by the linking of metal atoms by the tib ligands and two dicarboxylate ligands in 2. (b, c) Views of the2D structure of 2. The two chains are shown in different colors (dark yellow and violet, with dark green and orange cobalt atoms) and the linkingthird dicarboxylate are shown in sky blue. Hydrogen atoms and free solvent molecules have been removed for clarity.

Figure 5. Thermal ellipsoid probability plot of the basic unit of 3.Hydrogen atoms and free solvent molecules have been removed forclarity. Thermal ellipsoids are at the 30% probability level.

Figure 6. For complex 3 (a) the network arrangement obtained by the linking of metal atoms by the 1,4-phda ligands only. (b) The networkarrangement obtained by linking of metal atoms by the tib ligands only. Hydrogen atoms and water molecules have been removed for clarity.

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The differences in the structures of 2 and 4 arise not onlyfrom the different coordination behavior of the metal ions, butalso in the linking patterns of the basic 1D array (the linkingwithin these arrays being almost identical) into the higherdimension. The 1D arrays have three layers of metal ionsrunning parallel to each other. If we identify them as upper,middle and lower layers, then in 2 half of the upper layer ofmetal atoms joins to the half of the upper layer of the atomsfrom an adjacent chain. The linking pattern for the lower layeris also similar. In other words the arrays of the metal atomsstack side-by-side to form the 2D structure. For 4 however,all of the atoms in the upper layer of the array join to cor-responding atoms of the lower layer of an adjacent chain(Figure S6, Supporting Information).Structure Description of [Mn(tib)2(H2O)2]n·(1,4-phdaH)2n·

(H2O)4n (5). This complex crystallizes in the monoclinic spacegroup P21/n and has a 2D coordination structure based onMn(II) ions and μ2-bridging tib ligands, as well as a 3Dhydrogen bonding network based on monoanionic 1,4-phdaH,coordinated and free water molecules. The asymmetric unit ofthe structure (Figure 9) is made from a Mn(II) ion with halfoccupancy, a tib ligand, one coordinated water molecule, onemonoanionic 1,4-phdaH, and two free water molecules. Eachmetal ion is hexacoordinated with octahedral coordination

geometry. Two opposing positions in the octahedron are takenup by two symmetry generated water molecules [Mn(1)−O(1W), 2.2127(14) Å]. Similarly the other four coordinationsites are occupied by two N(1) and N(3) atoms from differenttib molecules trans to each other [Mn(1)−N(1), 2.2730(13) Å;Mn(1)−N(3), 2.2459(13) Å]. This coordination structureproduces a 2D arrangement (Figure 10) of atoms with one of

the imidazole nitrogen atom on the tib ligand remaining free(available for hydrogen bonding). The net can be described as afour-connected uninodal net (sql/Shubnikov tetragonal planenet) with point (Schlafli) symbol {44.62}.The hydrogen bonding network is much more interesting

(Table S2, Supporting Information). First, the monoanionic1,4-phdaH moieties form a 1D hydrogen bonded network bylinking with the neighboring such units through the interactionof the deprotonated and nondeprotonated carboxylic acidgroups, and these chains run along the crystallographic c axis. Inaddition, these chains are also linked in a complicated mannerby hydrogen bonding with the coordinated and free watermolecules to produce a 3D network (Figure 11) that penetratesthrough the 2D coordinated network described previously. Thetwo different networks are joined by the hydrogen bondingthrough the coordinated water molecules.This complex may seem to be odd, given that in the other

complexes the carboxylates do take part in metal coordination.But the 2D coordination network with μ2-bridging tib ligandsand coordinated water molecules have been previously re-ported as the complexes [Mn(tib)2(H2O)2](ClO4)2·2H2O and[Mn(tib)2(H2O)2](NO3)2 by Sun et al.15a Therefore, the 2D

Figure 7. Thermal ellipsoid probability plot of the basic unit of 4.Hydrogen atoms and free solvent molecules have been removed forclarity. Thermal ellipsoids are at the 30% probability level.

Figure 8. Ball and stick representation of the 2D arrangement of 4.Hydrogen atoms and free solvent molecules have been removed forclarity.

Figure 9. Thermal ellipsoid probability plot of the basic unit of 5.Thermal ellipsoids are at the 30% probability level.

Figure 10. Ball and stick representation of the 2D coordinationarrangement of 5. Hydrogen atoms and free solvent molecules havebeen removed for clarity.

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coordination network may represent a stable form of crystalarrangement for the two components involved, limiting the roleof the dicarboxylic acid involved.Magnetic Behavior. Complexes 1 and 2. The dc magnetic

susceptibility measured on polycrystalline samples of 1 and 2under an applied field of 0.1 T is shown in Figure 12, as χMT vs

T plots (where χM is the molar magnetic susceptibility per CoII

ion). At room temperature (300 K), the χMT values for the twocomplexes are 2.47 and 2.20 cm3 K mol−1, respectively, con-siderably higher than expected for an uncoupled CoII ion (χMT =1.875 cm3 K mol−1 for an S = 3/2 ion with g = 2.0). The highervalues of χMT at room temperature can be attributed to higher gvalues or orbital contribution to the magnetic moment(commonly found for CoII ions). The χMT values graduallydecrease upon lowering the temperature to about 100 K andbelow this temperature falls very rapidly to reach 1.74 and1.70 cm3 K mol−1 respectively for 1 and 2 at 2 K. For both ofthe complexes, the neighboring Co(II) ions are separated by9−13 Å, which is very high for effective exchange amongthe paramagnetic centers. Therefore, the effects of the non-quenched orbital contribution for the metal ions are probablyresponsible for the gradual decrease of the χMT values onlowering the temperature.Complex 3. The magnetic properties of 3, in the form of

χMT vs T per Co(II) ion (H = 0.1 T) are presented in Figure13. The room temperature χMT value of 2.65 cm3 K mol−1 ismuch greater than the expected value for an isolated Co(II) ionwith S = 3/2 spin, which may be attributed to the presence ofnonquenched orbital contributions. The χMT value decreasesgradually with temperature (χMT value at 100 K is 2.36 and at

50 K is 2.02 cm3 K mol−1) to reach 1.18 cm3 K mol−1 at 2 K. Inthe temperature range 14−18 K, a slight maxima is observed inthe χMT vs T plot. This anomaly is most probably due to smallamounts of undetectable (through elemental analysis andPXRD measurements) impurities present in the sample, whichare often present in samples prepared by hydrothermalmethods. We prepared several batches of the sample formagnetic studies and found the anomaly to be minimum withthe complex prepared at 150 °C (although the complex pre-pared at 130 °C, like the other four complexes, is of very highpurity, but from magnetic studies we found that for complex 3,the sample prepared at 150 °C is most pure and the magneticbehavior is highly reproducible).The magnetic exchange system in the complex is highly

complicated in nature. In the structure of this complex, twoCo(II) ions are bridged by μ1,1- and μ1,3-carboxylato groups, forwhich antiferromagnetic coupling may be expected. However,the other metal ions are bridged at long distances by thedicarboxylate and tib ligands. So, the overall magnetic behaviorof the complex can be explained by antiferromagnetic interac-tions among the two Co(II) ions (carboxylate bridged) andthree noninteracting paramagnetic metal centers, which resultsin the lowering of the χMT values with decreasing temperatures.The nonquenched orbital contributions of the metal ions alsoprobably play a part in the magnetic behavior of the complex.

Complex 5. The magnetic properties (H = 0.1 T) in theform of χMT vs T plot per Mn(II) ion (Figure S11, SupportingInformation) reveal that complex 5 is paramagnetic in naturewith a constant χMT = 4.51 cm3 K mol−1 in the temperaturerange 2−300 K. Fitting of the 1/χM vs T data using Curie−Weiss equation (2−300 K) also provided the value for C =4.503(2) cm3 K mol−1 (Figure S9, Supporting Information)and Weiss constant θ ∼ 0 K [−0.05(2) K]. This result is con-sistent with the fact that in the structure of 5 the neighboringparamagnetic Mn(II) ions are separated by 10−13 Å throughtib bridges. This may also point out the fact that tib bridgesprobably do not play any major role in the magnetic exchangesin the complexes 1−3.

Thermal Stabilities of the Complexes. Thermogravi-metric analyses (TGA) were carried out to probe the thermalstabilities of the complexes, and the results are shown in FigureS12 [Supporting Information]. Complex 1 shows a weight lossof 3.42% below 150 °C corresponding to the release of freewater molecules (calcd 3.30%). The residue shows no weightloss up to 330 °C (as there are no coordinated solvent mole-cules), and the decomposition of the complex starts at ∼335 °C.

Figure 11. Ball and stick representation of the hydrogen bonding(shown by fragmented lines) arrangement of 5. The tib moleculeshave been removed for clarity.

Figure 12. Plots of χMT vs T for complexes 1 and 2 in the temperaturerange of 2−300 K with the applied field 0.1 T. The solid lines areguide for the eyes.

Figure 13. Plots of χMT vs T for complex 3 in the temperature rangeof 2−300 K and with an applied field 0.1 T.

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A total weight loss of 4.00% was observed for 2 below thetemperature 240 °C, in two steps, which can be attributed to theloss of both the noncoordinated (90−130 °C) and coordinatedwater molecules (calcd 3.97%), and the residue is stable up toabout 340 °C, above which it starts to decompose. Similarly,complex 3 also lost about 8.10% of its weight below 255 °C, intwo steps, due to the loss of noncoordinated and coordinatedwater molecules (calcd 7.96%), and the organic ligands in theresidue starts to decompose at about 350 °C. Complex 4 has nocoordinated water molecules and accordingly lost 5.23% (calcd5.16%) of weight due to the loss of the free water moleculesbelow 135 °C. The residue shows no further weight loss up toabout 375 °C and decomposes above this temperature. Complex5 lost 6.50% of weight below 125 °C corresponding to the loss offree water molecules (calcd 6.54%) and a total of 9.95% ofweight below 200 °C due to further loss of the coordinated watermolecules (calcd 9.81%). The residue starts to decompose justabove 300 °C.Photoluminescence Property. Because of their potential

applications as photoactive materials, the photoluminescenceproperties of the Zn(II) coordination polymers have beenwidely investigated.22 The emission spectra of complex 4 inthe solid state and at room temperature has been shown inFigure 14, along with that of the free ligand tib for comparison.

No obvious luminescence was observed under the sameexperimental conditions for the free dicarboxylic acids or theother four complexes.The free ligand tib display photoluminescence with emission

maxima at 408 nm (λex = 360 nm) in accordance with previousreports.15 This emission band can be assigned to π*→ π transi-tion of tib.15 Complex 4 shows a similar but broader emissionband with emission maxima at 415 nm (λex = 360 nm).As the Zn(II) ion with d10 configuration is difficult to oxidize

or reduce, the emission band of 4 cannot be attributed to eithermetal-to-ligand (MLCT) or ligand-to-metal charge transfer(LMCT).23 Thus, the emission may be assigned primarily tothe intraligand and ligand-to-ligand charge transition(LLCT).15r Although 1,3-phdaH2 did not show any emissionin the free state, however, in the complex it may take part in theemission process being modified by the coordination ofthe carboxylates to the metal ions. The small red shift observedfor the emission maximum between the complex and the li-gand (tib) may originate from the influence of the ligandcoordination.

■ CONCLUDING REMARKSIn conclusion, we have described the synthesis and character-ization of five novel 3d-metal extended complexes, obtainedfrom the use of isomeric phenylenediacetates (phda) and the1,3,5-tris(1-imidazolyl)benzene (tib) ligand. The flexible natureof the dicarboxylates along with the semirigid tib linkerproduced new topological networks through serendipitousassemblies. Interestingly, the three isomeric dicarboxylates withthe same metal ion [Co(II)] under identical conditions resultedin complexes with different metal to tib ratios. They producedunique structural features with double-layered and inter-penetrated 2D networks, and a 3D complex with highly com-plicated network topology. The Co(II) and Zn(II) complexeswith the 1,3-phda ligand, although having roughly identicalbasic building units, produced two unique topological networksthrough different organizations in the higher dimension. Theserendipitous nature of the assemblies is even more visible inthe Mn(II) complex, in which the dicarboxylic acid loses onlyone proton and does not take part in coordination but stillproduces a complicated hydrogen bonded network with watermolecules. The magnetic studies on complexes 1−3 and 5revealed that the tib ligand is a very poor coupler of magneticexchange. Complex 4 was found to show a broad photo-luminescence spectrum with the λmax at 415 nm.Predesign in metal organic assemblies, although particularly

attractive due to the possible control of the resulting structures,has a limited role in discovering new structural topologies. Theserendipitous method that has been advocated through theexamples in this article provides support for the abovestatement and is now widely accepted as a proficient syntheticapproach in the field of MOFs and CPs.

■ ASSOCIATED CONTENT*S Supporting InformationX-ray crystallographic data in CIF format, PXRD patterns,details of crystallographic and magnetic measurement data.CCDC reference numbers 941011−941015. This material isavailable free of charge via the Internet at http://pubs.acs.org.

■ AUTHOR INFORMATIONCorresponding Author*E-mail: psm@ipc.iisc.ernet.in. Fax: 91-80-23601552. Tel: 91-80-22933352.NotesThe authors declare no competing financial interest.

■ ACKNOWLEDGMENTSS.M. gratefully acknowledges the Council of Scientific andIndustrial Research, New Delhi, India, for the award of aResearch Fellowship. Authors also thank the Department ofScience and Technology (DST), New Delhi for financialsupport.

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Figure 14. Emission spectra of the free ligand tib and complex 4 in thesolid state at room temperature.

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