TIMPZ: An Exquisite Building Block for Metal/Hydrogen Coordination Polymers
The novel polynitrogenated ligand tetra‐[4(5)‐imidazoyl]pyrazine (TIMPZ, 1) and its pincer complex of FeII are described. This ligand has an outstanding ability to aggregate in 1D‐superstructures by means of hydrogen bonding or metal chelation. TIMPZ shows an unprecedented conformational control ove...
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| Published in: | European journal of inorganic chemistry Vol. 2019; no. 17; pp. 2291 - 2294 |
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| Format: | Journal Article |
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| Abstract | The novel polynitrogenated ligand tetra‐[4(5)‐imidazoyl]pyrazine (TIMPZ, 1) and its pincer complex of FeII are described. This ligand has an outstanding ability to aggregate in 1D‐superstructures by means of hydrogen bonding or metal chelation. TIMPZ shows an unprecedented conformational control over the supramolecular assembly. Metal or hydrogen coordination switches the conformation of peripheral rings driving the assembly preferences. For [Fen(TIMPZ)n+1]2n+ complexes, UV/Vis spectroscopy shows a bathochromic shift of the main visible absorption band with higher “n” values. TIMPZ also has hydrogen‐bond triggered excited‐state intramolecular proton transfer (ESIPT) fluorescence, which is completely inhibited by chelation with transition metals.
Polynitrogenated ligand TIMPZ shows an unprecedented conformational control over the supramolecular assembly triggered by metal or hydrogen coordination. [Fen(TIMPZ)n+1]2n+ pincer complexes and 1D coordination polymers feature bathochromic shift of the main visible absorption band with increasing “n” values. (TIMPZ)n 1D aggregates as large as 22 units, showing ESIPT fluorescence, were detected. |
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| AbstractList | The novel polynitrogenated ligand tetra‐[4(5)‐imidazoyl]pyrazine (TIMPZ,
1
) and its pincer complex of Fe
II
are described. This ligand has an outstanding ability to aggregate in 1D‐superstructures by means of hydrogen bonding or metal chelation. TIMPZ shows an unprecedented conformational control over the supramolecular assembly. Metal or hydrogen coordination switches the conformation of peripheral rings driving the assembly preferences. For [Fe
n
(TIMPZ)
n
+1
]
2n+
complexes, UV/Vis spectroscopy shows a bathochromic shift of the main visible absorption band with higher “
n
” values. TIMPZ also has hydrogen‐bond triggered excited‐state intramolecular proton transfer (ESIPT) fluorescence, which is completely inhibited by chelation with transition metals. The novel polynitrogenated ligand tetra‐[4(5)‐imidazoyl]pyrazine (TIMPZ, 1) and its pincer complex of FeII are described. This ligand has an outstanding ability to aggregate in 1D‐superstructures by means of hydrogen bonding or metal chelation. TIMPZ shows an unprecedented conformational control over the supramolecular assembly. Metal or hydrogen coordination switches the conformation of peripheral rings driving the assembly preferences. For [Fen(TIMPZ)n+1]2n+ complexes, UV/Vis spectroscopy shows a bathochromic shift of the main visible absorption band with higher “n” values. TIMPZ also has hydrogen‐bond triggered excited‐state intramolecular proton transfer (ESIPT) fluorescence, which is completely inhibited by chelation with transition metals. Polynitrogenated ligand TIMPZ shows an unprecedented conformational control over the supramolecular assembly triggered by metal or hydrogen coordination. [Fen(TIMPZ)n+1]2n+ pincer complexes and 1D coordination polymers feature bathochromic shift of the main visible absorption band with increasing “n” values. (TIMPZ)n 1D aggregates as large as 22 units, showing ESIPT fluorescence, were detected. The novel polynitrogenated ligand tetra‐[4(5)‐imidazoyl]pyrazine (TIMPZ, 1) and its pincer complex of FeII are described. This ligand has an outstanding ability to aggregate in 1D‐superstructures by means of hydrogen bonding or metal chelation. TIMPZ shows an unprecedented conformational control over the supramolecular assembly. Metal or hydrogen coordination switches the conformation of peripheral rings driving the assembly preferences. For [Fen(TIMPZ)n+1]2n+ complexes, UV/Vis spectroscopy shows a bathochromic shift of the main visible absorption band with higher “n” values. TIMPZ also has hydrogen‐bond triggered excited‐state intramolecular proton transfer (ESIPT) fluorescence, which is completely inhibited by chelation with transition metals. |
| Author | So, Fernanda W. Y. Kubota, Lauro T. Oliveira, Thiago V. Nome, René A. Ligiéro, Carolina B. P. Barragan, José T. C. Miranda, Paulo C. M. L. Fontes, Chárbel C. F. |
| Author_xml | – sequence: 1 givenname: Carolina B. P. orcidid: 0000-0002-1944-9030 surname: Ligiéro fullname: Ligiéro, Carolina B. P. organization: University of Campinas – sequence: 2 givenname: Thiago V. orcidid: 0000-0002-8553-3409 surname: Oliveira fullname: Oliveira, Thiago V. organization: University of Campinas – sequence: 3 givenname: Chárbel C. F. orcidid: 0000-0003-2256-2496 surname: Fontes fullname: Fontes, Chárbel C. F. organization: University of Campinas – sequence: 4 givenname: José T. C. orcidid: 0000-0002-5863-6461 surname: Barragan fullname: Barragan, José T. C. organization: University of Campinas – sequence: 5 givenname: Fernanda W. Y. orcidid: 0000-0002-6203-0112 surname: So fullname: So, Fernanda W. Y. organization: University of Campinas – sequence: 6 givenname: Lauro T. orcidid: 0000-0001-8189-2618 surname: Kubota fullname: Kubota, Lauro T. organization: University of Campinas – sequence: 7 givenname: René A. orcidid: 0000-0003-4804-3395 surname: Nome fullname: Nome, René A. organization: University of Campinas – sequence: 8 givenname: Paulo C. M. L. orcidid: 0000-0002-6418-3614 surname: Miranda fullname: Miranda, Paulo C. M. L. email: miranda@iqm.unicamp.br organization: University of Campinas |
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| Cites_doi | 10.1021/ja048421u 10.1021/cr200174w 10.1002/adma.201102046 10.1016/S0010-8545(00)80009-0 10.1021/cr3002824 10.1039/C4CC07109C 10.1038/nmat4766 10.1021/ic0509229 10.1002/chem.201601766 10.1039/C6OB01604A 10.1016/j.tetlet.2009.04.098 10.1021/ja508592f 10.1021/ja000921 10.1021/cr100160e 10.1039/C4CP03223C 10.1021/jp300340t 10.1021/acs.jpclett.7b03175 10.1021/jp4061297 10.1021/ja0552139 10.1021/jacs.5b13524 |
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| References | 2011 2006; 111 128 2018; 9 2013; 113 1971; 7 2004; 126 2005 2016; 44 138 2014 2014 2012 2011; 16 50 116 23 2009; 50 2016; 14 2016 2000; 22 122 2012 2014 2017; 112 136 16 2013; 117 e_1_2_5_6_4 e_1_2_5_9_1 e_1_2_5_6_3 e_1_2_5_8_1 e_1_2_5_10_2 e_1_2_5_11_1 e_1_2_5_6_2 e_1_2_5_7_1 e_1_2_5_10_1 e_1_2_5_6_1 e_1_2_5_13_1 e_1_2_5_3_3 e_1_2_5_5_1 e_1_2_5_11_2 e_1_2_5_12_1 e_1_2_5_3_2 e_1_2_5_4_1 e_1_2_5_2_2 e_1_2_5_3_1 e_1_2_5_2_1 |
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| Snippet | The novel polynitrogenated ligand tetra‐[4(5)‐imidazoyl]pyrazine (TIMPZ, 1) and its pincer complex of FeII are described. This ligand has an outstanding... The novel polynitrogenated ligand tetra‐[4(5)‐imidazoyl]pyrazine (TIMPZ, 1 ) and its pincer complex of Fe II are described. This ligand has an outstanding... |
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| SubjectTerms | Absorption spectra Assembly Chelation Coordination polymers Fluorescence Hydrogen Hydrogen bonding Hydrogen bonds Inorganic chemistry Iron Ligands Metal–organic frameworks Superstructures Supramolecular chemistry Switches Transition metals |
| Title | TIMPZ: An Exquisite Building Block for Metal/Hydrogen Coordination Polymers |
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