Ligand Coordination Site-Directed Assembly of Copper(I) Iodide Complexes of ((Pyridyl)-1-pyrazolyl)pyridine

Abstract

A series of ((pyridinyl)-1H-pyrazolyl)­pyridine (pypzpy) ligands in which the pyrazolyl ring at 1- and 3-positions is modified by two 2-, 3-, or 4-pyridyl groups were prepared. Reaction of CuI with 2-(1-(pyridin-2-yl)-1H-pyrazolyl)­pyridine (2,2′-pypzpy) in MeCN at room temperature or solvothermal reaction of the same components at 120 °C afforded one binuclear complex [{(2,2′-pypzpy)­Cu}­(μ-I)]2 (1). Treatment of CuI with 3-(1-(pyridin-2-yl)-1H-pyrazolyl)­pyridine (3,2′-pypzpy) at room temperature or at 120 °C produced one-dimensional (1D) polymer [{Cu3(μ3-I)3}­(μ-3,2′-pypzpy)] n (2) and one two-dimensional (2D) polymer [{Cu2(μ-I)­(μ3-I)}2(3,2′-pypzpy)2] n (3), respectively. Similar reactions of CuI with 4-(1-(pyridin-2-yl)-1H-pyrazolyl)­pyridine (4,2′-pypzpy) at room temperature or at 150 °C yielded one 1D polymeric complex [{Cu­(μ3-I)}2(4,2′-pypzpy)2{Cu­(μ-I)}2] n (4). Complexes [{Cu3(μ3-I)3}­(μ-2,3′-pypzpy)] n (5), [(CuI)­(μ-2,3′-pypzpy)]2 (6), [(Cu2I2)­(3,3′-pypzpy)] (7), [(CuI)­(4,3′-pypzpy)] (8), [{Cu­(μ3-I)}2(μ-2,4′-pypzpy)2{Cu­(μ-I)}2] n (9), [(CuI)­(3,4′-pypzpy)] (10), and [(CuI)­(μ-4,4′-pypzpy)] n (11) could be isolated by solution reactions or solvothermal reactions of CuI with 2-, 3-, 4-(1-(pyridin-3-yl)-1H-pyrazolyl)­pyridine (2,3′-, 3,3′-, 4,3′-pypzpy), or 2-, 3-, 4-(1-(pyridin-4-yl)-1H-pyrazolyl)­pyridine (2,4′-, 3,4′-, 4,4′-pypzpy). Compounds 1–11 were characterized by IR, elemental analysis, powder X-ray diffraction, and single-crystal X-ray crystallography. Complex 1 contains a normal [Cu­(μ-I)]2 dimeric structure. Complexes 2 and 5 consist of a unique displaced staircase chain [Cu2(μ3-I)2] n . Complex 3 has a 2D network formed by linking chairlike [Cu2(μ-I)­(μ3-I)]2 units with two pairs of 3,2′-pypzpy bridges. Complexes 4 and 9 have a rare 1D triple chain, in which one internal 1D ladder-like chain [Cu2(μ3-I)2] n is connected with two zigzag chains [Cu­(μ-I)] n via 4,2′-pypzpy or 2,4′-pypzpy ligands. Compound 6 consists of two [CuI] units interconnected by two 2,3′-pypzpy ligands. Compound 11 contains a 1D chain assembled by monomeric [CuI] units and 4,4′-pypzpy ligands. The luminescence properties of 1–11 in solid state were also investigated at room temperature. These results offer an interesting insight into how the coordination sites of the pypzpy ligands do exert great impact on their coordination modes, the coordination spheres of the Cu­(I) centers, the formation of the [Cu n I n ] motifs and the topological structures of the final complexes.

Copper‐ or Thermally Induced Divergent Outcomes: Synthesis of 4‐Methyl 2H‐Chromenes and Spiro‐4H‐Pyrazoles

“…After gradient elevation of the reaction temperature to 90 °C, the reaction gave 2 a and 4 in 44 and 55 % conversions, respectively (Scheme a and Figure S3), which further confirmed that 3 H ‐pyrazole 6 is the intermediate in this transformation. In addition, the formation of 4 in this case, which did not need the catalyst, led us to deduce that the anion exchange (Ts − /I − ) and/or coordination of the copper catalyst with 6 might occurred first before the dinitrogen exclusion/nucleophilic addition took place to give 2 a . In this context, the commercially available CuOTf was employed to the template reaction (Scheme b), and from this study, both the copper complex 6′′ and the trifyl addition product 2′ were observed by ESI‐MS (Figure S4 and S5), but effort trying to purify 2′ by column chromatography failed due to the instability of this compound.…”

Photoluminescent Copper(I) Complex Based on 3‐(2‐(Cyclohexylthio)ethoxy)pyridine: Synthesis, Structure, and Physical Properties

“…In recent years, the Cu(I) complexes, with d 10 electronic configuration, have been attracting interest due to their diverse structures and photophysical properties . Copper(I) iodide clusters are able to adopt a variety of coordination modes varying from isolated complexes to three‐dimensional (3D) networks including various structural motifs such as Cu 2 I 2 , cubane or stairstep Cu 4 I 4 , hexagonal Cu 6 I 6 , heptanuclear Cu 7 I 7 , infinite one‐dimensional (1D), and double‐stranded stair (CuI) n . Copper(I) complexes have been studied for their potential application in display devices as a result of their high efficiency, low toxicity, and low‐cost .…”

Molecular sieving using metal–polymer coordination membranes in organic media

“…24 The complexation ability of copper(I) with aromatic nitrogen moieties has been investigated in numerous studies, which reported diverse structures such as metal coordination spheres and cluster formations. [25][26][27] In particular, copper(I) iodide complexes have emerged as useful materials for organic light emitting diodes, sensors, imaging technologies, and solar cells. 27 In this research, we designed MPC membranes and investigated their structure-property relationship through thorough materials characterization, molecular modeling, and nano-ltration in organic media.…”