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
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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

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

DOI:https://doi.org/10.1021/acs.inorgchem.7b00290

Pag. 5141-5151

Malaestean Yurii1, Kravtsov Victor1, Lipkowski Janusz2, Cariati Elena34, Righetto S.4, Marinotto D.4, Forni Alessandra3, Fonari Marina1
 
1 Institute of Applied Physics, Academy of Sciences of Moldova,
2 Cardinal Stefan Wyszyński University in Warsaw,
3 ISTM-CNR, Istituto di Scienze e Tecnologie Molecolari,
4 University of Milan
 
 
Disponibil în IBN: 13 februarie 2023


Rezumat

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). 

Cuvinte-cheie
Cuprous Iodide, Xantphos, complex

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<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&prime;-bipyridine (bpy), resulted in one two-dimensional and two three-dimensional new coordination networks. Starting from Cu(NO<sub>3</sub>)<sub>2</sub>&middot;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>]&middot;I<sub>5</sub>}<sub>n</sub>&nbsp;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>&nbsp;and new brown {[Cu<sup>II</sup>(NO<sub>3</sub>)(bpy)<sub>2</sub>]&middot;I<sub>3</sub>&middot;(dmf&middot;H<sub>2</sub>O)}<sub>n</sub>&nbsp;coordination polymers. By using either Cu(CH<sub>3</sub>COO)<sub>2</sub>&middot;H<sub>2</sub>O or Cu(BF<sub>4</sub>)<sub>2</sub>&nbsp;as starting materials, both known forms, yellow [(Cu<sup>I</sup>I)<sub>2</sub>(bpy)]<sub>n</sub>&nbsp;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>&nbsp;represents the missing member in the row of two-dimensional coordination networks with general formula [Cu<sup>I</sup>X(pyz)]<sub>n</sub>&nbsp;(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 (&Delta;E = 70 meV).&nbsp;</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>