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Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism.

Liu K, Shen ZR, Li Y, Han SD, Hu TL, Zhang DS, Bu XH, Ruan WJ - Sci Rep (2014)

Bottom Line: During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations.Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures.Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

View Article: PubMed Central - PubMed

Affiliation: 1] Department of Chemistry, TKL of Metal and Molecule-Based Material Chemistry and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China [2].

ABSTRACT
Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

No MeSH data available.


Related in: MedlinePlus

χmT vs T plots of S-MeCN, S-MeOH and S-DMF at 1 kOe.Inset: M/NμB vs H plots of S-MeCN, S-MeOH and S-DMF at 2 K.
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f5: χmT vs T plots of S-MeCN, S-MeOH and S-DMF at 1 kOe.Inset: M/NμB vs H plots of S-MeCN, S-MeOH and S-DMF at 2 K.

Mentions: As shown in Fig. 5, the magnetic susceptibility of S-MeCN, S-MeOH and S-DMF were measured at 1 kOe and the temperature range of 2–300 K. The χmT curves of the three samples displayed similar trend and decreased gradually from 300 k to 2 K. The χm−1 vs T plots in the temperature range of 50–300 K (Fig. 6) gave the C = 3.59 cm3 K mol−1, 3.49 cm3 K mol−1, 3.18 cm3 K mol−1 and θ = −8.11 K, −16.02 K, −8.51 K for the S-MeCN, S-MeOH and S-DMF, respectively, according to the Curie-Weiss law. The negative value of θ indicated the antiferromagnetic coupling between the metal centres and/or the spin-orbit coupling effect of Co(II) cations55. Their magnetization curves at 2 K (Fig. 5, inset) also demonstrated the antiferromagnetic coupling. Interestingly, the CPs displayed morphology dependent magnetic properties (Fig. 5). For one thing, it is known that the size of CPs existed: S-MeCN < S-MeOH or S-DMF, so the smallest CPs had the largest C and θ values. For another, S-MeOH and S-DMF had the same crystalline structure but different morphology, and it is shown that their magnetic curves and related parameters are distinct from each other.


Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism.

Liu K, Shen ZR, Li Y, Han SD, Hu TL, Zhang DS, Bu XH, Ruan WJ - Sci Rep (2014)

χmT vs T plots of S-MeCN, S-MeOH and S-DMF at 1 kOe.Inset: M/NμB vs H plots of S-MeCN, S-MeOH and S-DMF at 2 K.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4129412&req=5

f5: χmT vs T plots of S-MeCN, S-MeOH and S-DMF at 1 kOe.Inset: M/NμB vs H plots of S-MeCN, S-MeOH and S-DMF at 2 K.
Mentions: As shown in Fig. 5, the magnetic susceptibility of S-MeCN, S-MeOH and S-DMF were measured at 1 kOe and the temperature range of 2–300 K. The χmT curves of the three samples displayed similar trend and decreased gradually from 300 k to 2 K. The χm−1 vs T plots in the temperature range of 50–300 K (Fig. 6) gave the C = 3.59 cm3 K mol−1, 3.49 cm3 K mol−1, 3.18 cm3 K mol−1 and θ = −8.11 K, −16.02 K, −8.51 K for the S-MeCN, S-MeOH and S-DMF, respectively, according to the Curie-Weiss law. The negative value of θ indicated the antiferromagnetic coupling between the metal centres and/or the spin-orbit coupling effect of Co(II) cations55. Their magnetization curves at 2 K (Fig. 5, inset) also demonstrated the antiferromagnetic coupling. Interestingly, the CPs displayed morphology dependent magnetic properties (Fig. 5). For one thing, it is known that the size of CPs existed: S-MeCN < S-MeOH or S-DMF, so the smallest CPs had the largest C and θ values. For another, S-MeOH and S-DMF had the same crystalline structure but different morphology, and it is shown that their magnetic curves and related parameters are distinct from each other.

Bottom Line: During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations.Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures.Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

View Article: PubMed Central - PubMed

Affiliation: 1] Department of Chemistry, TKL of Metal and Molecule-Based Material Chemistry and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China [2].

ABSTRACT
Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

No MeSH data available.


Related in: MedlinePlus