Trinuclear Cobalt Based Porous Coordination Polymers Showing

Dec 2, 2008 - are associated together to give a tunable 8-connected topological framework, viz. ..... The V-shaped ip spacers connect the Co3(CO2)8]2 ...
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CRYSTAL GROWTH & DESIGN

Trinuclear Cobalt Based Porous Coordination Polymers Showing Unique Topological and Magnetic Variety upon Different Dicarboxylate-like Ligands

2009 VOL. 9, NO. 2 1066–1071

Feng Luo, Yun-xia Che, and Ji-min Zheng* Department of Chemistry, Nankai UniVersity, Tianjin 300071, China ReceiVed August 14, 2008; ReVised Manuscript ReceiVed October 23, 2008

ABSTRACT: One-pot solvothermal self-assembly is employed to prepare a series of Co3 based porous coordination polymers, viz. 1, [H2N(CH3)2]2[Co3(ip)4] · H2O, 2, [H2N(CH3)2]2[Co3(bdc)4] · (DMF)2, 3, [H2N(CH3)2]2[Co3(bpdc)4] · (CH3OH)2(DMF)1.5, where ip, bdc, bpdc, and DMF are 1,3-benzenedicarboxylate, 1,4-benzenedicarboxylate, 4,4′-biphenyldicarboxylate, and N,N′-dimethylformamide, respectively. Via different organic connectors such as ip, bdc, and bpdc, such Co3 molecular building blocks (MBB), [Co3(CO2)8]2-, are associated together to give a tunable 8-connected topological framework, viz. 42464 for 1, 36414576 for 2, and 36418536 for 3. Upon the geometry and the length of organic connectors, their corresponding porosity occupied by c counterions plus solvent molecules also can be tunable, for example, with the consideration of [H2N(CH3)2]+ counterions, the solvent-accessible volume is 460.2 Å3 for 1, equal to 23.9% of the cell volume, 3320.4 Å3 for 2, equal to 56.3% of the cell volume, 4107.2 Å3 for 3, equal to 50% of the cell volume. Notably, besides these outstanding features of tunable 8-connected topology and porosity, their magnetic properties such as ferromagnetic behavior without magnetic ordering for 1, spin-canting and metamagnetic behavior with magnetic ordering for 2, as well as spin-canting, metamagnetic, and spin-glass behavior with magnetic ordering for 3 also can be tunable. Introduction To date, methodologies for the rational and controlled design and preparation of metal-organic frameworks (MOFs), especially the porous coordination polymers (PCPs), are still one of the most focused areas of research, due to their aesthetically intriguing topology architectures and highly promising chemical and physical applications in many fields such as gas storage, selective separation, catalytic purposes, and so on.1 From the considerations of energy sources and cost, exploring and developing multifunctional PCPs will be the best and most sensible choice. As we know, properties are derived from the natural structure, and also can be subtly moderated by slight structure changes. Recently, this natural relationship between structure and function has been recognized and achieved by one potential platform, viz. well-defined functional molecular building blocks (MBBs), a platform that is effective to assemble and construct multifunctional PCPs.2 The best examples are the MOF-5 and MIL-102 series, where the functional tetrahedral Zn4 and trigonal Cr3 or Al3 MBBs are explored and developed, and their pore size can be rationally controlled by the length of the organic spacers.3 Similarly, the Co3 pinwheel MBB, having the formula Co3(CO2)6(sol)2, where sol is the terminal coordinated solvent molecules located on the two side Co(II) sites, is also realized to construct magnetic PCPs. And the well-defined structures are honeycomb and R-Po (pcu) net, based on the 6-connected Co3(CO2)6(sol)2 pinwheel MBB.4 By replacing sol molecules with bridging diamine or dipyridyl linkers, the 6-connected MBB will be extended to be 8-connected MBB and the corresponding 8-connected framework will be the final results (Scheme 1). Notably, this kind of 8-connected net has been shown to afford efficient H2 storage, mainly because of the narrow channel with a triangular cross-section rather than the obviously straight channels.5 If the formal charge for the well-defined Co3(CO2)6(sol)2 or Co3(CO2)6(diamine/or dipyridyl)2 pinwheel MBB is neutral, then the resulting net is also * To whom correspondence should be addressed. Tel: +86-22-23507950; e-mail: [email protected].

Scheme 1

neutral. If introducing dicarboxylate-like linkers into the two side Co(II) sites, then it is obvious that another 8-connected net will be created. However, such resulting 8-connected net will have a negative formal charge, as the corresponding Co3(CO2)6(CO2)2 (in the following discussion, it is simplified to be Co3(CO2)8) pinwheel MBB affords a formal charge of -2. It is accepted that systemic and comparative research based on the controlled assembly of magneto-MBBs may give further insight into understanding the macroscopical magnetic behavior and the fundamental study of the microcosmic magnetic exchange mechanism, and via appropriate variation of the geometrical and electronic properties of organic linkers, it may be possible to fine-tune the magnetic interaction pathway and the final magnetic behavior. In the literature, much effort has been paid to the exploration of magnetic change upon the absence or presence of solvent molecules.6 By contrast, to date, the case of tunable magnetic behavior based on well-defined magneto-MBB upon different organic linkers is still scarce. Herein, via one-pot solvothermal synthesis, we select three kinds

10.1021/cg800895g CCC: $40.75  2009 American Chemical Society Published on Web 12/02/2008

Trinuclear Cobalt Based Porous Coordination Polymers

Crystal Growth & Design, Vol. 9, No. 2, 2009 1067

Table 1. The Crystal Data and Structure Refinements for Complexes 1-3

a

compound

1

2

3

formula fw temp(K) cryst syst space group a (Å) b (Å) c (Å) β (°) Z vol (Å3) density (mg/m3) R1 and ωR2 [I > 2(I)]a,b

C36H34Co3N2O17 943.46 298(2) monoclinic P21/c 11.586(2) 14.543(3) 13.117(6) 119.57(2) 2 1922.3(10) 1.626 0.0322, 0.0728

C42H46Co3N4O18 1071.63 113(2) monoclinic C2/c 32.997(7) 9.7187(19) 18.392(4) 92.25(3) 4 5894(2) 1.190 0.1182, 0.3121, 0.0634S, 0.1724S

C66.5H66.5Co3N3.5O19.5 1403.55 294(2) monoclinic P2/c 22.550(10) 14.187(7) 25.681(12) 92.096(9) 4 8210(7) 1.045 0.2256, 0.4838, 0.1401S, 0.3393S

R1 ) Σ|Fo - Fc|/Σ|Fo|. b ωR2 ) Σ[ω(Fo2 - Fc2)2]/Σ[ω(Fo2)2]1/2. S indicates that the value is obtained after the Squeeze program. Table 2. Selected Co-O Bond Lengths (Å), Co-O-Co Angles (°), and Intra-MBB Metal-to-Metal Distance (Å) for 1-3a 1

Co(1)-O(1) Co(1)-O(6)#2 Co(1)-O(8)#3 Co(1)-O(4) Co(1)-O(3) Co(1)-O(7)#3 Co(2)-O(2) Co(2)-O(2)#4 Co(2)-O(5)#5 Co(2)-O(5)#2 Co(2)-O(3) Co(2)-O(3)#4 Co(2)-O(3)-Co(1) Co1-Co2

2 1.9989(15) 2.0121(16) 2.1157(17) 2.1325(18) 2.2038(16) 2.2343(17) 2.0367(14) 2.0367(14) 2.1028(16) 2.1028(16) 2.1499(16) 2.1499(16) 108.47(7) 3.5329(6)

Co(1)-O(4)#3 Co(1)-O(2) Co(1)-O(7) Co(1)-O(5) Co(1)-O(6) Co(2)-O(1) Co(2)-O(1)#4 Co(2)-O(3)#3 Co(2)-O(3)#5 Co(2)-O(7) Co(2)-O(7)#4 Co(1)-O(7)-Co(2) Co1-Co2

3 1.9606(3) 2.0067(4) 2.0112(4) 2.0220(4) 2.3413(6) 2.0581(4) 2.0581(4) 2.0599(5) 2.0599(5) 2.1585(3) 2.1585(3) 102.806(17) 3.2602(7)

Co(1)-O(9) Co(1)-O(8) Co(1)-O(6)#1 Co(1)-O(4)#2 Co(1)-O(3)#2 Co(2)-O(15)#3 Co(2)-O(11) Co(2)-O(13)#4 Co(2)-O(2) Co(2)-O(1) Co(3)-O(5)#1 Co(3)-O(14)#4 Co(3)-O(12) Co(3)-O(7) Co(3)-O(1) Co(3)-O(3)#2 Co(3)-O(1)-Co(2) Co(3)#5-O(3)-Co(1)#5 Co2-Co3 Co1-Co3

1.9900(9) 1.9964(7) 1.9975(7) 2.0351(10) 2.3852(9) 1.9577(8) 2.0099(7) 2.0184(7) 2.0572(10) 2.3691(9) 2.0697(7) 2.0833(7) 2.1055(6) 2.1161(6) 2.1495(7) 2.1707(7) 108.76(3) 107.16(4) 3.6753(16) 3.6683(16)

a The symmetry codes: 1: #2 -x, y - 1/2, -z + 1/2. #3 -x + 1, y + 1/2, -z + 3/2. #4 -x, -y, -z + 1. #5 x, -y + 1/2, z + 1/2. 2: #3 x, -y + 2, z - 1/2. #4 -x + 1/2, -y + 3/2, -z. #5 -x + 1/2, y - 1/2, -z +1/2. 3: #1 x, -y + 2, z + 1/2. #2 x, y - 1, z. #3 x + 1, y, z. #4 x, -y + 1, z - 1/2. #5 x, y + 1, z.

Scheme 2. The Coordinated Modes of ip, bdc, and bpdc

of dicarboxylate-like linkers, viz. H2ip, H2bdc, and H2bpdc, where ip, bdc, and bpdc are 1,3-benzenedicarboxylate, 1,4benzenedicarboxylate, 4,4′-biphenyldicarboxylate, respectively, to assemble the [Co3(CO2)8]2- pinwheel MBB based PCPs, and to further explore the relationship of function and structure. As a result, the expected 8-connected [Co3(CO2)8]2- pinwheel MBB and the corresponding 8-connected nets are constructed. Interestingly, their framework topology, pore size, and magnetic behavior display outstanding diversification upon these dicarboxylate-like linkers. Experimental Section Materials and Instruments. All reagents were bought from commercial sources without further purification. Elemental analysis

(EA) was carried out on Elementar Vario EL III microanalyzer; TG analysis was performed with a heating rate of 5 °C/min under N2 using a NETZSCH STA 449C simultaneous TG-DSC instrument. Magnetic measurements were carried out with a Quantum Design (SQUID) magnetometer MPMS-XL-5. Synthesis of 1, 2, 3. An N,N′-dimethylformamide (DMF)/CH3OH (5:1) solution of CoCl2, and H2ip (or H2bdc, or H2bpdc) in a ratio of 1:1.25 was sealed in a Teflon reactor, and heated at 160 °C for two days, and then cooled to room temperature at 3 °C/h. Subsequently, purple block crystals were obtained in 42% yield based on Co for 1, 65% yield for 2, and 54% yield for 3. The single crystal samples of 1-2 are air-stable, while that of 3 are sensitive to the air; if exposed in air, then they will undergo the slow efflorescence process. Element analysis (%) for 1: calc: C 45.83, H 3.63, N 2.97; found: C 45.84, H 3.65, N 2.96; for 2: calc: C 47.07, H 4.33, N 5.23; found: C 47.12, H 4.36, N 5.28; for 3: calc: C 56.91, H 4.78, N 3.49; found: C 56.96, H 4.71, N 3.41. X-ray Crystallography. Suitable single crystals of 1-3 was selected and mounted in air onto thin glass fibers. Accurate unit cell parameters were determined by a least-squares fit of 2θ values, and intensity data were measured on a Rigaku R-AXIS RAPID IP area diffractometer with Mo KR radiation (λ ) 0.71073 Å) at room temperature. The intensities were corrected for Lorentz and polarization effects as well as for empirical absorption based on multiscan technique, all structures were solved by Direct methods and refined by full-matrix least-squares fitting on F2 by SHELX-97. All non-hydrogen atoms were refined with anisotropic thermal parameters. The H atoms are added by calculation. For 3, due to the disorder of DMF molecules, the presence of 1.5 DMF molecules is confirmed by EA and TG analysis. For 2 and 3, the [H2N(CH3)2]+ counterions and solvent molecules (such as DMF in 2, DMF and CH3OH

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Figure 1. The tunable 8-connected topology upon different organic spacers such as ip, bdc, bpdc: the up/distinct [Co3(CO2)8]2 MBBs; the middle/ schematic description of the 8-connected[Co3(CO2)8]2 MBB; the bottom/schematic description of each anionic 8-connected net.

Figure 2. Schematic description of the 2-fold interpenetrating net in 3. in 3) are badly disordered, which causes large R1 and ωR2 values. Then, the Platon Squeeze program is applied to treat these badly disordered counterions and solvent molecules, leading to better R1 and ωR2 values. Crystal data and structure refinement for these polymers are summarized in Table 1. Selected Co-O bond lengths, Co-O-Co angles, and intraMBB metal-to-metal distance are listed in Table 2. CCDC number: 642848 for 1, 692473-692474 for 2 and 2S, 692475-692476 for 3 and 3S. Note: S indicates that the data is obtained after the Squeeze program.

Results and Discussion Description of Structures. The coordinated modes of ip, bdc, and bpdc are listed in Scheme 2. The following structure discussion is based on CIF files for 1-3. The formula of polymers 1-3 is further confirmed by elemental analysis (EA) and TG studies. Crystal Structure of Polymers 1-3. Polymers 1-3 hold a similar [Co3(CO2)8]2 MBB, but different topological frameworks

(see Figure 1). Thereby, the comparing research of these [Co3(CO2)8]2 MBBs and resulting topological framework appears important. Within the [Co3(CO2)8]2 MBB in 1-3, the middle Co(II) site holds CoO6, octahedral geometry is completed by six ip, bdc, or bpdc oxygens, whereas the two terminal Co(II) sites show different coordination geometries: in 1, the two cobalt sites also have CoO6, octahedral geometry is completed by six ip oxygens; for 2 and 3, four bdc or bdpc oxygens ligate to the two cobalt sites to give the CoO4, tetrahedral geometry, together with the weak Co-O coordinated bond such as Co(1)-O(6)/ 2.3413(6) Å for 2 and Co(1)-O(3)#2 (x, y - 1, z) /2.3852(9) Å, Co(2)-O(1)/ 2.3691(9) Å for 3. The Co-O bond lengths in 1-3 are comparable (see Table 2). Each intra-MBB Co-Co pair is bridged by one ip, bdc, or bpdc carboxylate oxygen, and two ip, bdc, or bpdc carboxyl groups. The Co-O-Co angles and intra-MBB Co-Co distances are also listed in Table 2, where the corresponding values for 2 are obviously smaller than that for 1 and 3, due to the different coordinated modes of one of the ip, bdc, or bpdc carboxyl groups that afford µ2:η2:η1 for 1 and 3, but µ2:η2:η0 for 2. The coordinated modes of ip, bdc, and bpdc are listed in Scheme 2: µ4:η1:η1:η1:η1, µ3:η1:η2:η1:η1 for ip, µ4:η1:η1:η1:η1, µ4:η2:η0:η2:η0, µ2:η1:η1:η1:η1 for bdc, µ4: η1:η1:η1:η1, µ4:η1:η0:η1:η0, µ4:η2:η1:η2:η1 for bpdc, where η means the oxygen coordinated mode of ip, bdc, and bpdc carboxyl groups. Further, these [Co3(CO2)8]2 MBBs are associated together via ip, bdc, or bpdc connectors to give the anionic frameworks. Interestingly, polymer 3 allows two such identical anionic frameworks to interpenetrate each other (see Figure 2). The total volume of void space (occupied by [H2N(CH3)2]+ counterions and solvent molecules) estimated by Platon is 460.2 Å3 for 1, equal to 23.9% of the cell volume, 3320.4 Å3 for 2, equal to 56.3% of the cell volume, and 4107.2 Å3 for 3, equal to 50% of the cell volume. Without the consideration of [H2N(CH3)2]+ counterions, the potential solvent-accessible volume evaluated

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Crystal Growth & Design, Vol. 9, No. 2, 2009 1069

Table 3. The Detailed Comparison among Polymers 1-3 MBB 1 2 3

connectors geometry of Co(II) 2-

[Co3(CO2)8] [Co3(CO2)8]2[Co3(CO2)8]2-

ip bdc bpdc

octahedral octahedral, tetrahedral octahedral, tetrahedral

coordinated mode of ligands 1

1

1

1

1

2

1

1

µ4:η :η :η :η , µ3:η :η :η :η µ4:η1:η1:η1:η1, µ4:η2:η0:η2:η0 µ2:η1:η1:η1:η1 µ4:η1:η1:η1:η1, µ4:η1:η0:η1:η0, µ4:η2:η1:η2:η1

by Platon is 48 Å3 for 1, equal to 2.5% of the cell volume, 2486.2 Å3 for 2, equal to 42.2% of the cell volume, and 3175 Å3 for 3, equal to 38.7% of the cell volume, which suggests the highly potential porous materials of 2 and 3.7 From a topological point of view, polymers 1-3 feature the same 8-connected anionic net built on the 8-connected [Co3(CO2)8]2 MBBs. However, further insight into these 8-connected anionic nets via topos40 program8 suggests the different 3D matrixes for 1-3: each 8-connected [Co3(CO2)8]2 MBB in 1 has the 42464 short symbol, 43.43.4.4.43.4.43.4.4.4.43.4.43. 4.43.4.43.4.43.4.43.43.43.4 long symbol, and TD10 2331; that in 2 has the 36414576 short symbol, 3.3.3.3.3.3.4.4.4.4.4. 4.4.4.4.4.4.4.4.4.52.52.52.52 long symbol, and TD10 431; whereas in 3, it has the 36418536 short symbol, 3.3.3.3.3.3.4.4.4.4. 4.4.4.4.4.4.4.4.4.4.4.4.4.4 long symbol, and TD10 124. It is obviously that the topology of 1 is a bcu-type CsCl net. In the literature, the 8-connected networks are still rare because the construction of such networks is severely hampered both by the number of available coordination sites and by the sterically demanding nature of many ligands. However, because of recent

Figure 3. The TG plot of 1-3.

Figure 4. The χMT vs T, and inserted χM vs T plots of 1-3.

potential porosity (Å3 per unit cell)

topology

48 2486.2 3175

42464 36414576 36418536

advances in crystal engineering, a variety of new 8-connected networks with the 42068, 36414576, 334155842, and 354115864 topologies, as well as self-penetrating 424563 topology, have been reported.9 Thus, to our best knowledge, it is believed that polymer 3 featuring the 8-connected 36418536 topology is a new type of 8-connected net, while it is also the first time that the framework topology built on similar MBBs can be fine-tuned by different organic spacers. Effect of Protonated Cationic Amines Templates. As we known, the use of positive-charged organic templates, such as commonly tetraalkylammonium cations or protonated cationic amines, also called structure-directing agents, to direct the selfassembly of molecular precursors into extended frameworks is widely found in inorganic framework materials. However, there is still limited research focused on the one-pot self-assembly of PCPs based on well-defined MBBs upon positive-charged organic structure-directing molecules.10 Herein, polymers 1-3 are prepared by the one-pot self-assembly of well-defined [Co3(CO2)8]2 MBBs with different organic connectors. It is believed that the one-pot formation of [Co3(CO2)8]2 MBB should depend on the positive-charged organic structure-directing molecules, viz. [H2N(CH3)2]+, which are derived from the in situ formation form DMF. The location of these [H2N(CH3)2]+ templates is shown in S1, viewed down [100], [010], and [001]. Effect of Organic Connectors. It is well-known that the 3D matrix of MOFs can be fine-tuned by the selecting suitable geometry of organic connectors.11 Herein, upon similar [Co3(CO2)8]2 MBBs, the V shaped ip connectors result in the 42464 net, whereas the linear bdc or bpdc spacers generate the elegant 36414576 or 36418536 nets, indicating the tunable effect of organic connectors on the resulting 3D matrix of MOFs. As discussed above, it is obviously that the potential porosity for polymers 1-3 shows the 3 > 2 > 1 sequence, mainly due to the various geometry and length of ip, bdc, and bpdc spacers. The detailed comparisons among polymers 1-3 are listed in Table 3. TG Research. Polymer 1 lost the free water molecule at 30-125 °C (exp. 1.8%, calc. 1.8%), and the following thermal behavior after 210 °C as traced by TG analysis may be the loss of HN(CH3)2 molecules and the succedent decomposition of the host skeleton. For 2 and 3, the first major loss is ascribed to be DMF (exp. 13.4%, calc. 13.6%) or DMF plus CH3OH (exp. 12.6%, calc. 12.4%) at 30-250 °C or 30-165 °C, respectively. Similarly, the following thermal behavior as traced by TG analysis indicates the loss of HN(CH3)2 molecules and the succedent decomposition of the host skeleton. As shown in Figure 3, it is clear that the thermal behavior of 1-3 is similar, but due to the thermostability diversity of ip, bdc, and bpdc, polymer 3 obviously shows the higher thermostability. Magnetic Properties. The temperature-dependent magnetic susceptibility data of polymers 1-3 was measured for crystal samples at an applied magnetic field of 1000 Oe in the temperature range of 2-300 K. The plots of χMT and χM vs T of these compounds are shown in Figure 4. The χMT values at room temperature for 1-3, 9.21 cm3 mol-1 K, 9.98 cm3 mol-1 K, 9.29 cm3 mol-1 K, respectively, are obviously larger than the expected values of 5.63 cm3 mol-1 K, the sum of three magnetism-isolated Co(II) ions with g ) 2.0, S ) 3/2, due to

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Figure 5. (a) the M vs H plots of 1-3 at 2 K; (b) the hysteresis loop of 1-3; (c) the dM/dH vs H plot of 2; (d) the dM/dH vs H plot of 3.

Figure 6. The AC magnetic susceptibilities of 1, left, 2, middle, and 3, right.

spin-orbit coupling of Co(II) ions.12 This situation is common for Co(II) ions. The outline at 18-300 K for 1, 65-300 K for 2, and 46-300 K for 3 suggests somewhat antiferromagnetic interactions, although the consideration of the spin-orbit coupling withdraw of Co(II) ions cannot be excluded. Furthermore, this situation has an upturn: for 1, it does not reach the max until 2 K (11.86 cm3 mol-1 K), whereas for 2 and 3, they get the max at 50 K (7.66 cm3 mol-1 K) and 25 K (8.50 cm3 mol-1 K), respectively, which indicates the onset of ferromagnetic behavior, possibly due to ferromagnetic interactions, or spin-canting effects.12 The succedent decrease for 2 and 3 should be derived from the inter-MBB antiferromagnetic interactions and/or zero field splitting (ZFS).12 At 2 K, the M vs H measurements among 0-50 kOe are given as Figure 5. For 1, the M values increase quickly at low field and trends to saturation at high field with the M value of 8.98 Nβ, which is comparable with the expected ferromagnetic coupling values

of 9 Nβ for three Co(II) ions, whereas for 2 and 3, their M values increase laggardly at low field and sharply increase at high field but without saturation. At 50 kOe, polymers 2-3 have M values of 5.19 Nβ and 3.91 Nβ; this M value is far below the expected ferromagnetic coupling values of 9 Nβ for three Co(II) ions. Thus, it is believed that the χMT vs T abnormality at low temperature for 1 should be derived from ferromagnetic interactions, and the decrease at 18-300 K is due to the spin-orbit coupling withdraw of Co(II) ions. By contrast, the comment of ferromagnetic behavior induced by spin-canting effect rather than ferromagnetic interactions is more suitable for the χMT vs T abnormality at low temperature for 2 and 3.12 In the literature, such phenomenon, ferromagnetic abnormality at low temperature induced by a spin-canting effect, is common in Co(II)-containing compounds.6,13 Interestingly, such M vs H outline of 2 and 3 also indicates the metamagnetic behavior, as evidenced by the dM/dH vs H plot with the critical field of

Trinuclear Cobalt Based Porous Coordination Polymers

650 Oe for 2 and 1000 Oe for 3 (Figure 5c,d).14 Further, ac magnetic susceptibilities for 1 without any max in χM′ and χM′′ suggest the absence of any magnetic ordering (Figure 6), and the hysteresis loop (Figure 6b) denotes a coercive field of 20 Oe and a remnant magnetization of 0.012 Nβ.12 By contrast, polymer 2 affords the frequency-independent max in χM′ at 45 K but without the max in χM′′, indicative of the antiferromagnetic ordering with the critical temperature about 45 K, whereas 3 has a slight frequency-dependent max both in χM′ and χM′′, indicative of the ferromagnetic ordering with the critical temperature around 20 K and spin-glass behavior.6,12,13 Similarly, polymers 2 and 3 show the coercive field of 100 Oe for 2 and 50 Oe for 3, remnant magnetization of 0.035 Nβ for 2 and 0.019 Nβ for 3. As discussed above, it is clear that, in this system, the macroscopical magnetic behavior based on the magnetic [Co3(CO2)8]2 MBBs can be easily tuned upon the variety of organic spacers. Of course, other factors such as the presence of a [H2N(CH3)2]+ counterion and solvent molecule that affect the macroscopical magnetic behavior cannot be excluded. From the magnetism-structure point of view, the special magnetic varieties of them are mainly dependent on the distinct cobalt coordination environments, Co-O-Co angles of each [Co3(CO2)8]2 MBB.

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(3)

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Conclusions Three kinds of dicarboxylate-like connectors, viz. ip, bdc, and bpdc, are employed to combine with Co(II) ions to carry out the one-pot solvothermal self-assembly of well-defined Co3(CO2)8]2 MBB based PCPs. As a result, polymers 1-3 are obtained. The geometry and length of ip, bdc, and bpdc cause the difference or modification for each corresponding Co3(CO2)8]2 MBB and the succedent 3D matrix, potential porosity, as well as magnetic properties. The V-shaped ip spacers connect the Co3(CO2)8]2 MBBs to give the common 42464 CsCl net, potential porosity of 48 Å3 per unit cell, and macroscopical ferromagnetic interactions without any magnetic ordering. By contrast, the linear bdc spacers connect the Co3(CO2)8]2 MBBs to create the uncommon 36414576 net, potential porosity of 2486.2 Å3 per unit cell, and macroscopical antiferromagnetic interactions with spin-canting, metamagnetic behavior and magnetic ordering at 45 K; the longer linear bpdc connectors link the Co3(CO2)8]2 MBBs to generate the unique 36418536 net, potential porosity of 3175 Å3 per unit cell, and macroscopical antiferromagnetic interactions with spin-canting, metamagnetic, spin-glass behavior and magnetic ordering around 22 K. To some extent, this work, for the first time, has demonstrated an easy and effective approach to fine-tune the physical and chemical properties of well-defined Co3(CO2)8]2 MBB based PCPs.

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Acknowledgment. This work was supported by the National Natural Science Foundation of China under Project (50572040).

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Supporting Information Available: Crystallographic data in CIF format; some figures are included. This material is available free of charge via the Internet at http://pubs.acs.org.

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