Lewis-Base Adducts of Group 11 Metal(I) Compounds. XLIII. Synthesis and Structural Systematics of 1 : 1 Copper(I) Halide/Nitrogen Base Adducts as [(N-base)1(CuX)1]∞ 'Split-Stair' Polymers (X = Cl, Br, I; N-Base = Acridine, Quinaldine and 2,6-Dimethyl- and 2,4,6-Trimethyl-Pyridine)

Abstract

The complete array of single strand ('split-stair') polymers for the 1 : 1 system CuX/monodentate nitrogen base, L, all X= Cl, Br, I, has now been synthesized and structurally characterized by using the highly hindered pyridine bases, L= acridine and quinaldine . Similar polymers, [ LCuX ] ∞, are also obtained with L = 2,6-dimethylpyridine for X = Cl, Br (but not I which is a dimer , [LCuI2CuL]), and for L = 2,4,6- trimethylpyridine, X = Br, I (but not Cl, which is ionic [CuL2]+[CuCl2]-). A general feature of all polymeric structures, although diverse in space group and not isomorphous in respect of polymer disposition, is the presence of a short crystallographic axis (about 4 � ) as the unit translational repeat distance.

Substituent Influence on Structural and Luminescent Diversities of Cu3(pyrazolate)3-CunIn Coordination Supramolecular Isomers

“…Each Cu 2 I 2 unit connects four Cu 3 ( L4 ) 3 units, and each Cu 3 ( L4 ) 3 unit connects two Cu 2 I 2 units, leaving one 4-pyridyl group in every Cu 3 ( L4 ) 3 unit vacant in such a structure. The bond parameters in Cu 2 I 2 Py 4 units are similar to those reported structures (Table S1 in the Supporting Information). ,− Interestingly, the vacant 4-pyridyl group in the Cu 3 ( L4 ) 3 unit further coordinate to one of the Cu atoms in another Cu 3 ( L4 ) 3 unit along the b crystallography axis, leading to the formation of a 3-D framework (Figure c–e). As shown in Figure , the N–Cu distance is about 2.244(1) Å, much longer than the normal N–Cu distance, and the N­(Pz)–Cu–N­(Pz) angle is about 164.6(1)°, as reported in our previous report .…”

“…Multinuclear copper­(I)/silver­(I)-based clusters have been widely used to construct photofunctional coordination materials in many fields such as lighting, , sensing, − optical devices, photocatalysis, − and other areas. , Among them, CuI-based clusters have been extensively reported to show fascinating structural diversity from the well-known rhombic Cu 2 I 2 ,− and cubic Cu 4 I 4 − to polynuclear aggregates and even polymers, − depending on the nature of the ligands , and synthesis procedures . Owing to the cuprophilicity, heavy atom effect, rich valence electrons of copper and iodine atoms, and electronic effect of organic ligands, CuI-based clusters show striking emission behaviors such as thermochromism and mechanochromism. − Trinuclear planar M 3 Pz 3 (M = Cu­(I), Ag­(I), or Au­(I), Pz = pyrazolate) chromophores, − on another note, have also attracted much attention as they exhibit rich photophysical and photochemical properties thanks to the intra- and/or intermolecular Cu···Cu interactions , and π-acid···base interactions. − …”

Cu4I4 Clusters Supported by P∧N-type Ligands: New Structures with Tunable Emission Colors

“…The Cu1A–Cu2A distances vary from 2.525(2) to 2.630(1) Å and are comparable to the equivalent Cu–Cu distance (2.576 Å) found in Cu 4 I 4 (dcpm) 2 . These Cu–Cu lengths are much shorter than those found in Cu 2 I 2 clusters coordinated with monodentate N-heteroaromatic ligands (2.872–3.303 Å) or diphosphine ligands (2.898 Å), but are comparable with those in bimetallic complexes supported by 1,2,3-triazole (2.530 Å), benzimidazoles (2.546 Å), 2-benzoyl pyridines (2.587 Å), 1,8-naphthyridine (2.61–2.63 Å), and related nitrogen donor ligands. − The steric constraints imposed by the bridging P ∧ N-ligands also influence the separation between A and B fragments in the five Cu 4 I 4 cores. Compounds 3 and 4 have the shortest distance between Cu1A–Cu2B (2.839(3) and 2.880(1) Å, respectively), whereas the longest separation is found in 5 (3.035(2) Å).…”

Short-Bite PNP Ligand-Supported Rare Tetranuclear [Cu4I4] Clusters: Structural and Photoluminescence Studies

“…The Cu1–Cu2 distance in 8 is shorter than the same in complex 7 but is comparable with the equivalent Cu–Cu distances found in analogous complexes reported in the literature (see Table ). The Cu–Cu bond length in complex 8 (2.5680(4) Å) is shorter than those found in the stair-step structure and Cu 2 I 2 clusters coordinated with bisphosphine ligands (2.898 Å) as well as monodentate N-heteroaromatic ligands (2.872–3.303 Å) but is comparable with those in bimetallic complexes containing bulky pyridyl ligands (2.557 Å), benzimidazoles (2.546 Å), imidazolyl pyridines (2.592 Å), phenanthroline (2.609 Å), 1,2,3-triazole (2.530 Å), and related nitrogen donor ligands (see Table ). The steric crowding imposed by the bridging bis(phosphonite) ligands in complexes 7 and 8 also influences the separation between the two fragments in the Cu 4 I 4 cores.…”