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 SM ISO690:2012MALAESTEAN, Yurii, KRAVTSOV, Victor, LIPKOWSKI, Janusz, CARIATI, Elena, RIGHETTO, S., MARINOTTO, D., FORNI, Alessandra, FONARI, Marina. Partial in Situ Reduction of Copper(II) Resulting in One-Pot Formation of 2D Neutral and 3D Cationic Copper(I) Iodide-Pyrazine Coordination Polymers: Structure and Emissive Properties. In: Inorganic Chemistry, 2017, vol. 56, pp. 5141-5151. ISSN 0020-1669. DOI: https://doi.org/10.1021/acs.inorgchem.7b00290 |
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  Inorganic Chemistry |
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| Volumul 56 / 2017 / ISSN 0020-1669 | |
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| DOI:https://doi.org/10.1021/acs.inorgchem.7b00290 | |
| Pag. 5141-5151 | |
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On the way to copper(I) iodide coordination polymers with specific luminescent properties, the in situ reduction of Cu(II) in the presence of KI and bidentate N-heteroatomic ligand, either pyrazine (pyz) or 4,4′-bipyridine (bpy), resulted in one two-dimensional and two three-dimensional new coordination networks. Starting from Cu(NO3)2·3H2O in the presence of pyz, successive precipitation of known yellow [(CuII)2(pyz)]n, new orange [CuII(pyz)]n, and new dark blue {[CuI(pyz)2]·I5}n polymeric solids was observed. Starting from the same salt in the presence of bpy resulted in the successive precipitation of known yellow [(CuII)2(bpy)]n and new brown {[CuII(NO3)(bpy)2]·I3·(dmf·H2O)}n coordination polymers. By using either Cu(CH3COO)2·H2O or Cu(BF4)2 as starting materials, both known forms, yellow [(CuII)2(bpy)]n and orange [CuII(bpy)]n, precipitated successively. The new solids were characterized by IR spectroscopy and X-ray analysis. [CuII(pyz)]n represents the missing member in the row of two-dimensional coordination networks with general formula [CuIX(pyz)]n (X = Cl, Br, I). Its steady state and time-resolved characterization together with DFT and TDDFT calculations revealed that the emission at room temperature is mainly delayed fluorescence originating from mixed singlet metal-to-ligand charge transfer and halide-to-ligand charge transfer states, while that at 77 K is phosphorescence, associated with the small singlet-triplet energy differences (ΔE = 70 meV). |
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| Cuvinte-cheie Cuprous Iodide, Xantphos, complex |
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<identifier identifierType='DOI'>10.1021/acs.inorgchem.7b00290</identifier>
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<creatorName>Malaeştean, I.L.</creatorName>
<affiliation>Institutul de Fizică Aplicată al AŞM, Moldova, Republica</affiliation>
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<creator>
<creatorName>Kravţov, V.H.</creatorName>
<affiliation>Institutul de Fizică Aplicată al AŞM, Moldova, Republica</affiliation>
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<creator>
<creatorName>Lipkowski, J.</creatorName>
<affiliation>Cardinal Stefan Wyszyński University in Warsaw, Polonia</affiliation>
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<creator>
<creatorName>Cariati, E.</creatorName>
<affiliation>ISTM-CNR, Istituto di Scienze e Tecnologie Molecolari, Italia</affiliation>
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<creator>
<creatorName>Righetto, S.</creatorName>
<affiliation>Universitatea din Milano, Italia, Italia</affiliation>
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<creator>
<creatorName>Marinotto, D.</creatorName>
<affiliation>Universitatea din Milano, Italia, Italia</affiliation>
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<creator>
<creatorName>Forni, A.</creatorName>
<affiliation>ISTM-CNR, Istituto di Scienze e Tecnologie Molecolari, Italia</affiliation>
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<creatorName>Fonari, M.S.</creatorName>
<affiliation>Institutul de Fizică Aplicată al AŞM, Moldova, Republica</affiliation>
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<titles>
<title xml:lang='en'>Partial in Situ Reduction of Copper(II) Resulting in One-Pot Formation of 2D Neutral and 3D Cationic Copper(I) Iodide-Pyrazine Coordination Polymers: Structure and Emissive Properties</title>
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<publisher>Instrumentul Bibliometric National</publisher>
<publicationYear>2017</publicationYear>
<relatedIdentifier relatedIdentifierType='ISSN' relationType='IsPartOf'>0020-1669</relatedIdentifier>
<subjects>
<subject>Cuprous Iodide</subject>
<subject>Xantphos</subject>
<subject>complex</subject>
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<date dateType='Issued'>2017-05-01</date>
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<description xml:lang='en' descriptionType='Abstract'><p>On the way to copper(I) iodide coordination polymers with specific luminescent properties, the in situ reduction of Cu(II) in the presence of KI and bidentate N-heteroatomic ligand, either pyrazine (pyz) or 4,4′-bipyridine (bpy), resulted in one two-dimensional and two three-dimensional new coordination networks. Starting from Cu(NO<sub>3</sub>)<sub>2</sub>·3H<sub>2</sub>O in the presence of pyz, successive precipitation of known yellow [(Cu<sup>I</sup>I)<sub>2</sub>(pyz)]<sub>n</sub>, new orange [Cu<sup>I</sup>I(pyz)]<sub>n</sub>, and new dark blue {[Cu<sup>I</sup>(pyz)<sub>2</sub>]·I<sub>5</sub>}<sub>n</sub> polymeric solids was observed. Starting from the same salt in the presence of bpy resulted in the successive precipitation of known yellow [(Cu<sup>I</sup>I)<sub>2</sub>(bpy)]<sub>n</sub> and new brown {[Cu<sup>II</sup>(NO<sub>3</sub>)(bpy)<sub>2</sub>]·I<sub>3</sub>·(dmf·H<sub>2</sub>O)}<sub>n</sub> coordination polymers. By using either Cu(CH<sub>3</sub>COO)<sub>2</sub>·H<sub>2</sub>O or Cu(BF<sub>4</sub>)<sub>2</sub> as starting materials, both known forms, yellow [(Cu<sup>I</sup>I)<sub>2</sub>(bpy)]<sub>n</sub> and orange [Cu<sup>I</sup>I(bpy)]<sub>n</sub>, precipitated successively. The new solids were characterized by IR spectroscopy and X-ray analysis. [Cu<sup>I</sup>I(pyz)]<sub>n</sub> represents the missing member in the row of two-dimensional coordination networks with general formula [Cu<sup>I</sup>X(pyz)]<sub>n</sub> (X = Cl, Br, I). Its steady state and time-resolved characterization together with DFT and TDDFT calculations revealed that the emission at room temperature is mainly delayed fluorescence originating from mixed singlet metal-to-ligand charge transfer and halide-to-ligand charge transfer states, while that at 77 K is phosphorescence, associated with the small singlet-triplet energy differences (ΔE = 70 meV). </p></description>
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