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![]() MALAESTEAN, 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 | |
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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<?xml version='1.0' encoding='utf-8'?> <oai_dc:dc xmlns:dc='http://purl.org/dc/elements/1.1/' xmlns:oai_dc='http://www.openarchives.org/OAI/2.0/oai_dc/' xmlns:xsi='http://www.w3.org/2001/XMLSchema-instance' xsi:schemaLocation='http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd'> <dc:creator>Malaeştean, I.L.</dc:creator> <dc:creator>Kravţov, V.H.</dc:creator> <dc:creator>Lipkowski, J.</dc:creator> <dc:creator>Cariati, E.</dc:creator> <dc:creator>Righetto, S.</dc:creator> <dc:creator>Marinotto, D.</dc:creator> <dc:creator>Forni, A.</dc:creator> <dc:creator>Fonari, M.S.</dc:creator> <dc:date>2017-05-01</dc:date> <dc:description xml:lang='en'><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></dc:description> <dc:identifier>10.1021/acs.inorgchem.7b00290</dc:identifier> <dc:source>Inorganic Chemistry () 5141-5151</dc:source> <dc:subject>Cuprous Iodide</dc:subject> <dc:subject>Xantphos</dc:subject> <dc:subject>complex</dc:subject> <dc:title>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</dc:title> <dc:type>info:eu-repo/semantics/article</dc:type> </oai_dc:dc>