Control of Copper(I) Iodide Architectures by Ligand Design:  Angular versus Linear Bridging Ligands

Abstract

A family of coordination polymers formed by the reaction of copper(I) iodide with a range of angular bidentate or tridentate N-donor ligands is reported. The framework polymers [CuI(dpt)](infinity) 1 [dpt = 2,4-bis(4-pyridyl)-1,3,5-triazine], [CuI(dpb)](infinity) 2 [dpb = 1,4-bis-(4-pyridyl)-benzene], [(CuI)3(dpypy)2](infinity) 3, [CuI(dpypy)](infinity) 4 [dpypy = 3,5-bis(4-pyridyl)-pyridine], and [Cu3I3(pypm)](infinity) 5 [pypm = 5-(4-pyridyl)pyrimidine] have been prepared and structurally characterized. It was found that the angular nature of the dpypy and dpt ligands favors the formation of discrete (CuI)2 dimeric subunits as observed in [CuI(dpt).MeCN](infinity) 1 and [(CuI)3(dpypy)2](infinity) 3. In contrast, reaction with the linear ligand dpb affords [CuI(dpb)](infinity) 2 which incorporates a one-dimensional (CuI)(infinity) chain structure. Moreover, the additional donor available on the central ring of the dpypy ligand generates a novel two-dimensional bilayer structure in 3, in contrast to the one-dimensional ribbon structure observed in the case of 1. Interestingly, the bilayer structure of 3 additionally exhibits 2-fold interpenetration. The reaction of CuI with dpypy produces not only 3 but a further product [CuI(dpypy)](infinity) 4 that has been characterized as a one-dimensional chain constructed from trigonal-planar Cu(I) centers bridged by bidentate dpypy ligands. Compound 5, [Cu3I3(pypm)](infinity), exhibits a highly unusual three-dimensional structure in which the pypm ligand bridges two-dimensional brick-wall (CuI)(infinity) sheets.

Syntheses and structures of copper complexes of 3-(6-(1H-pyrazol-1-yl)pyridin-2-yl)pyrazol-1-ide and their excellent performance in the syntheses of nitriles and aldehydes

“…The Cu(1)-I(1) (or Cu(1)-I(1A)) bond distance is relatively long (3.0250 (11) (2)-I distance (2.5258(7) Å) is shorter than that observed in [CuI-(dpypy)] n (2.5415(8); dpypy = 3,5-bis(4-pyridyl)pyridine). 22 The Cu(1)-N bond lengths vary from 1.938(3) Å to 2.062(4) Å, which are close to those in 3·2MeOH. In 3·2MeOH and 5, the two pzpypz − ligands also take a trans configuration, and their phenyl groups are twisted by 28.49°(3·2MeOH) and 37.24°(5), respectively.…”

Construction of [Cu n I n ]-based coordination polymers via flexible benzimidazolyl-based ligands

“…Anal. Calcd for C 30 [{Cu 2 (-I) 2 (ebbm) 2 }·2MeCN] n (3). Compound 3 (colorless plates) was prepared in a similar manner to that described for 2, using CuI (19 mg, 0.1 mmol) and ebbm (26 mg, 0.1 mmol) as starting materials in n-hexane (0.1 mL) and MeCN (2 mL).…”

“…Among the inorganic-organic hybrid materials, copper(I) salts, such as [Cu(MeCN) 4 ]ClO 4 , have attracted much attention [28]. Especially, copper(I) iodide have been employed as inorganic components in the construction of novel coordination polymers with various structural motifs such as rhomboid [Cu 2 (-I) 2 ] fragment [29][30][31], cubanelike or chairlike [Cu 4 ( 3 -I) 4 ] fragment [32][33][34], and zigzag [CuI] n chain [29,31,35]. These motifs could be further connected by N-heterocyclic linkers to form more complex [Cu n I n ]-based frameworks.…”

Reversible stimulus-responsive Cu(i) iodide pyridine coordination polymer

“…[20][21][22][23][24][25][26] The intra-chain CuÁ Á ÁCu Experimental details, crystallographic data and structure refinement details of all the compounds, additional data of X-ray studies on thermal variation parameters of compound 1, supramolecular interactions details and DFT calculations of 1 LT , 1 RT and 1a, and additional data of the studies on the device characterization based on compound 1. CCDC 1046598-1046600.…”