Copper(I) oligomers and polymers with dicyanobenzene and cyanopyridine ligands

Abstract

The reaction of [Cu(MeCN) 4 ]BF 4 with o-, m-, or p-dicyanobenzene (DCB) or o-, m-, or p-cyanopyridine (CPy) in the presence of two equivalents of PPh 3 produces DCB-or CPybridged copper(I) complexes. Cyclic dimers are formed for the ortho ligands, and zigzag polymers are formed using the para ligands. m-DCB produces a polymer, however m-CPy results in a cyclic trimer. Multiple lattice-bound solvates are formed upon crystallization of the o-DCB dimer from various solvents. A total of 11 X-ray crystal structures are reported for [Cu n (PPh 3) 2n (bridge) n ](BF 4) n •(solvent): bridge = o-DCB, n = 2, solvent (per dimer) = none, ½ CH 2 Cl 2 , CH 2 Cl 2 , 2 CHCl 3 /H 2 O, or 2 THF; bridge = m-DCB, n = ∞, solvent = none; bridge = p-DCB, n = ∞, solvent = CH 2 Cl 2 (two polymorphs), bridge = o-CPy, n = 2, solvent (per dimer) = 2 toluene; bridge = m-CPy, n = 3, solvent = none; bridge = p-CPy, n = ∞, solvent = ½ acetone. All complexes are photoluminescent with excitation in the range 340-400 nm. The meta complexes emit in the blue region, while the other complexes emit in the green. Dimer complexes of o-DCB exhibit structural flexibility in the central macrocyclic ring. Complexes of m-DCB and p-CPy show orientational disorder in the ligand. Polymeric complexes show helicity. Smaller Stokes

Silver(I) complexes with nitrile ligands: New materials with versatile applications

“…Distorted coordination is affected by the chelation of the nitrate anion in the asymmetric mode, where the longer Ag2–O5 bond is 2.560 Å long and the shorter one Ag2–O1 is equal to 2.300 Å. The Ag–O–N–Ag chain propagates along the a‐axis and exhibits a zigzag configuration characteristic for 1,4‐dcb complexes of 11 group metals 31 . The shortest Ag···Ag separation within the chain is 4.840 Å and between the chains it is 3.708 Å, which, being longer than the sum of the van der Waals radii of silver atoms (3.44 Å 32 ), excludes argentophilic interactions 33 .…”

“…The Ag-O-N-Ag chain propagates along the aaxis and exhibits a zigzag configuration characteristic for 1,4-dcb complexes of 11 group metals. 31 The shortest AgÁÁÁAg separation within the chain is 4.840 Å and between the chains it is 3.708 Å, which, being longer than the sum of the van der Waals radii of silver atoms (3.44 Å 32 ), excludes argentophilic interactions. 33 The arrangement of the polymer chains within the crystal is illustrated in Figure 4b.…”