Solvent-induced single-crystal-to-single-crystal transformation and tunable magnetic properties of 1D azido-Cu(ii) chains with a carboxylate bridge
By means of the solvent effect, three new azido-copper 1D coordination polymers, [Cu(4-aba)(N3)] (1), [Cu(4-aba)(N3)(CH3OH)] (2), and [Cu(4-aba)(N3)(C2H5OH)] (3) (4-aba = 4-azidobenzoic acid), were successfully prepared in the presence of Cu2+ ion, NaN3 and 4-azidobenzoic acid. Interestingly, 1 can be employed as a precursor and transformed to 2 and 3via the coordination of methanol or ethanol, respectively. Meanwhile, the identical products of 1, namely 1a and 1b, could be obtained from both 2 and 3 by a dealcoholized process. As a result, the geometric configurations of Cu(ii) ions vary from the tetracoordinated square-planar in 1 to the hexacoordinated octahedron in 2 or 3. Compound 1 displays a well-isolated 1D chain with dual-bridges of EO-azido and syn,syn-carboxylate, while isomorphic 2 and 3 are triple-bridged chain-like motifs containing EO-azido, syn,syn-carboxylate and μ2-alkanol. The structural transformations caused by the intervention of alkanol molecules modulate the intrachain Cu-Cu distances (3.570 for 1, 3.204 Å for 2 and 3.154 Å for 3) and Cu-N-Cu angles (127.3° for 1, 106.82° for 2 and 104.81° for 3). This modulation, however, further leads to different intrachain ferromagnetic interactions (J = 28.4 cm-1 for 1, 67.6 cm-1 for 2, 40.2 cm-1 for 3) that are qualitatively demonstrated by theoretical calculation. More importantly, the significant scenarios of magnetic ordering and slow magnetic relaxation, which are infrequent in most of the reported azido-copper cases, are only observed in 2 and 3, due to the distinct interchain networks among 1-3. In addition, heat-capacity measurements highlight the characteristics of long-range ferromagnetic ordering in 2 and 3.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2019 |
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| Erschienen: |
2019 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:48 |
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| Enthalten in: |
Dalton transactions (Cambridge, England : 2003) - 48(2019), 30 vom: 14. Aug., Seite 11268-11277 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Liu, Xiangyu [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 31.07.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1039/c9dt02031d |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM298787016 |
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| 100 | 1 | |a Liu, Xiangyu |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Solvent-induced single-crystal-to-single-crystal transformation and tunable magnetic properties of 1D azido-Cu(ii) chains with a carboxylate bridge |
| 264 | 1 | |c 2019 | |
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| 500 | |a Date Revised 31.07.2019 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a By means of the solvent effect, three new azido-copper 1D coordination polymers, [Cu(4-aba)(N3)] (1), [Cu(4-aba)(N3)(CH3OH)] (2), and [Cu(4-aba)(N3)(C2H5OH)] (3) (4-aba = 4-azidobenzoic acid), were successfully prepared in the presence of Cu2+ ion, NaN3 and 4-azidobenzoic acid. Interestingly, 1 can be employed as a precursor and transformed to 2 and 3via the coordination of methanol or ethanol, respectively. Meanwhile, the identical products of 1, namely 1a and 1b, could be obtained from both 2 and 3 by a dealcoholized process. As a result, the geometric configurations of Cu(ii) ions vary from the tetracoordinated square-planar in 1 to the hexacoordinated octahedron in 2 or 3. Compound 1 displays a well-isolated 1D chain with dual-bridges of EO-azido and syn,syn-carboxylate, while isomorphic 2 and 3 are triple-bridged chain-like motifs containing EO-azido, syn,syn-carboxylate and μ2-alkanol. The structural transformations caused by the intervention of alkanol molecules modulate the intrachain Cu-Cu distances (3.570 for 1, 3.204 Å for 2 and 3.154 Å for 3) and Cu-N-Cu angles (127.3° for 1, 106.82° for 2 and 104.81° for 3). This modulation, however, further leads to different intrachain ferromagnetic interactions (J = 28.4 cm-1 for 1, 67.6 cm-1 for 2, 40.2 cm-1 for 3) that are qualitatively demonstrated by theoretical calculation. More importantly, the significant scenarios of magnetic ordering and slow magnetic relaxation, which are infrequent in most of the reported azido-copper cases, are only observed in 2 and 3, due to the distinct interchain networks among 1-3. In addition, heat-capacity measurements highlight the characteristics of long-range ferromagnetic ordering in 2 and 3 | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Ma, Xiufang |e verfasserin |4 aut | |
| 700 | 1 | |a Yang, Jinhui |e verfasserin |4 aut | |
| 700 | 1 | |a Luo, Shuchang |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Zheng |e verfasserin |4 aut | |
| 700 | 1 | |a Ferrando-Soria, Jesús |e verfasserin |4 aut | |
| 700 | 1 | |a Ma, Yulong |e verfasserin |4 aut | |
| 700 | 1 | |a Shi, Quan |e verfasserin |4 aut | |
| 700 | 1 | |a Pardo, Emilio |e verfasserin |4 aut | |
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| 773 | 1 | 8 | |g volume:48 |g year:2019 |g number:30 |g day:14 |g month:08 |g pages:11268-11277 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1039/c9dt02031d |3 Volltext |
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