{"title":"由 2,6-吡啶二甲酰肼和 2,6-二乙酰基吡啶模板缩合得到的 Cu(II)、Co(III) 和 Ni(II) 四氮杂大环配合物：稳定性研究和在塑料上的着色性能","authors":"","doi":"10.1016/j.molstruc.2024.140021","DOIUrl":null,"url":null,"abstract":"<div><p>Completely conjugated 14-membered ring hexaaza ligand complexes of Cu(II), Co(III) and Ni(II) were synthesized by the template cyclo-condensation reaction of 2,6-diacetylpyridine and 2,6-pyridinedicarbohydrazide: [Cu(HL)Cl]·1.35H<sub>2</sub>O (<strong>1</strong>), [Cu(HL)Br]·CH<sub>3</sub>OH (<strong>2</strong>), [Cu(L)(H<sub>2</sub>O)]·4H<sub>2</sub>O (<strong>3</strong>), [Co(HL)Cl<sub>2</sub>]·CH<sub>3</sub>OH (<strong>4</strong>), (H<sub>3</sub>O)[Co(H<sub>2</sub>L)Cl<sub>2</sub>][Co(HL)Cl<sub>2</sub>]Cl<sub>2</sub>·H<sub>2</sub>O (<strong>5</strong>), [Co(HL)(SCN)<sub>2</sub>]·CH<sub>3</sub>OH (<strong>6</strong>)<strong>,</strong> [Ni(L)]·3H<sub>2</sub>O (<strong>7)</strong> and (H<sub>3</sub>O)[Ni(L)]Cl·H<sub>2</sub>O (<strong>8</strong>). The structure of all complexes derived from this novel diprotic macrocyclic ligand H<sub>2</sub>L (5,7-dimethyl-3,4,8,9-tetraaza-1,6(2,6)-dipyridinacyclodecaphane-4,7-diene-2,10-dione) were determined by single crystal X-ray diffraction method. The tetraaza 14-membered conjugated macrocycle is N<sub>4</sub>-tetracoordinated to metal, adopts an essentially planar configuration and forms four fused metallocycles rings, two five-membered and two six-membered chelates. The structures of the studied complexes reveal three isomers out of three possible: with a 5-6-5-6 order of alternation of metallocycles for <strong>1</strong>–<strong>6</strong>, the 5-5-6-6 isomer in <strong>8</strong> and the coexistence of two different isomers with 5-5-6-6 and 6-6-5-5 alternation of metallocycles in <strong>7</strong>. Based on the protonation state of the macrocyclic ligand, four forms of the ligand have been registered: bis-deprotonated L<sup>2−</sup> (compounds <strong>3, 7</strong> and <strong>8</strong>), monodeprotonated HL<sup>−</sup> (<strong>1, 2</strong> and <strong>4</strong>), neutral H<sub>2</sub>L (<strong>5</strong>) and for compound <strong>6</strong> tautomeric (amide → imidic acid) HL<sup>−</sup> form. The organisation of crystal structures <strong>1</strong>–<strong>8</strong> depends on the nature of the metal and the composition of the solvents and outer-sphere ions, but shows clear common features for the same type of metal. The hydrolytic study demonstrated a high stability of the Co(III) and Ni(II) complexes in acidic solutions and the most thermally stable are the complexes <strong>3</strong> and <strong>7</strong> with the limit of 350 °C for Ni(II) complex. Testing of the coloring properties of the [Ni(L)] (<strong>8</strong>) complex on plastics indicates a high coloring efficiency, especially for polyamide polymers.</p></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":null,"pages":null},"PeriodicalIF":4.0000,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Tetraaza macrocyclic complexes of Cu(II), Co(III) and Ni(II) derived from template condensation of 2,6-pyridinedicarbohydrazide and 2,6-diacetylpyridine: Stability investigation and coloring properties on plastics\",\"authors\":\"\",\"doi\":\"10.1016/j.molstruc.2024.140021\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Completely conjugated 14-membered ring hexaaza ligand complexes of Cu(II), Co(III) and Ni(II) were synthesized by the template cyclo-condensation reaction of 2,6-diacetylpyridine and 2,6-pyridinedicarbohydrazide: [Cu(HL)Cl]·1.35H<sub>2</sub>O (<strong>1</strong>), [Cu(HL)Br]·CH<sub>3</sub>OH (<strong>2</strong>), [Cu(L)(H<sub>2</sub>O)]·4H<sub>2</sub>O (<strong>3</strong>), [Co(HL)Cl<sub>2</sub>]·CH<sub>3</sub>OH (<strong>4</strong>), (H<sub>3</sub>O)[Co(H<sub>2</sub>L)Cl<sub>2</sub>][Co(HL)Cl<sub>2</sub>]Cl<sub>2</sub>·H<sub>2</sub>O (<strong>5</strong>), [Co(HL)(SCN)<sub>2</sub>]·CH<sub>3</sub>OH (<strong>6</strong>)<strong>,</strong> [Ni(L)]·3H<sub>2</sub>O (<strong>7)</strong> and (H<sub>3</sub>O)[Ni(L)]Cl·H<sub>2</sub>O (<strong>8</strong>). The structure of all complexes derived from this novel diprotic macrocyclic ligand H<sub>2</sub>L (5,7-dimethyl-3,4,8,9-tetraaza-1,6(2,6)-dipyridinacyclodecaphane-4,7-diene-2,10-dione) were determined by single crystal X-ray diffraction method. The tetraaza 14-membered conjugated macrocycle is N<sub>4</sub>-tetracoordinated to metal, adopts an essentially planar configuration and forms four fused metallocycles rings, two five-membered and two six-membered chelates. The structures of the studied complexes reveal three isomers out of three possible: with a 5-6-5-6 order of alternation of metallocycles for <strong>1</strong>–<strong>6</strong>, the 5-5-6-6 isomer in <strong>8</strong> and the coexistence of two different isomers with 5-5-6-6 and 6-6-5-5 alternation of metallocycles in <strong>7</strong>. Based on the protonation state of the macrocyclic ligand, four forms of the ligand have been registered: bis-deprotonated L<sup>2−</sup> (compounds <strong>3, 7</strong> and <strong>8</strong>), monodeprotonated HL<sup>−</sup> (<strong>1, 2</strong> and <strong>4</strong>), neutral H<sub>2</sub>L (<strong>5</strong>) and for compound <strong>6</strong> tautomeric (amide → imidic acid) HL<sup>−</sup> form. The organisation of crystal structures <strong>1</strong>–<strong>8</strong> depends on the nature of the metal and the composition of the solvents and outer-sphere ions, but shows clear common features for the same type of metal. The hydrolytic study demonstrated a high stability of the Co(III) and Ni(II) complexes in acidic solutions and the most thermally stable are the complexes <strong>3</strong> and <strong>7</strong> with the limit of 350 °C for Ni(II) complex. Testing of the coloring properties of the [Ni(L)] (<strong>8</strong>) complex on plastics indicates a high coloring efficiency, especially for polyamide polymers.</p></div>\",\"PeriodicalId\":16414,\"journal\":{\"name\":\"Journal of Molecular Structure\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.0000,\"publicationDate\":\"2024-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Structure\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022286024025304\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Structure","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022286024025304","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Tetraaza macrocyclic complexes of Cu(II), Co(III) and Ni(II) derived from template condensation of 2,6-pyridinedicarbohydrazide and 2,6-diacetylpyridine: Stability investigation and coloring properties on plastics
Completely conjugated 14-membered ring hexaaza ligand complexes of Cu(II), Co(III) and Ni(II) were synthesized by the template cyclo-condensation reaction of 2,6-diacetylpyridine and 2,6-pyridinedicarbohydrazide: [Cu(HL)Cl]·1.35H2O (1), [Cu(HL)Br]·CH3OH (2), [Cu(L)(H2O)]·4H2O (3), [Co(HL)Cl2]·CH3OH (4), (H3O)[Co(H2L)Cl2][Co(HL)Cl2]Cl2·H2O (5), [Co(HL)(SCN)2]·CH3OH (6), [Ni(L)]·3H2O (7) and (H3O)[Ni(L)]Cl·H2O (8). The structure of all complexes derived from this novel diprotic macrocyclic ligand H2L (5,7-dimethyl-3,4,8,9-tetraaza-1,6(2,6)-dipyridinacyclodecaphane-4,7-diene-2,10-dione) were determined by single crystal X-ray diffraction method. The tetraaza 14-membered conjugated macrocycle is N4-tetracoordinated to metal, adopts an essentially planar configuration and forms four fused metallocycles rings, two five-membered and two six-membered chelates. The structures of the studied complexes reveal three isomers out of three possible: with a 5-6-5-6 order of alternation of metallocycles for 1–6, the 5-5-6-6 isomer in 8 and the coexistence of two different isomers with 5-5-6-6 and 6-6-5-5 alternation of metallocycles in 7. Based on the protonation state of the macrocyclic ligand, four forms of the ligand have been registered: bis-deprotonated L2− (compounds 3, 7 and 8), monodeprotonated HL− (1, 2 and 4), neutral H2L (5) and for compound 6 tautomeric (amide → imidic acid) HL− form. The organisation of crystal structures 1–8 depends on the nature of the metal and the composition of the solvents and outer-sphere ions, but shows clear common features for the same type of metal. The hydrolytic study demonstrated a high stability of the Co(III) and Ni(II) complexes in acidic solutions and the most thermally stable are the complexes 3 and 7 with the limit of 350 °C for Ni(II) complex. Testing of the coloring properties of the [Ni(L)] (8) complex on plastics indicates a high coloring efficiency, especially for polyamide polymers.
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