catena-Poly[[di-μ-chloro-bis[(triphenylphosphine)silver(I)]]-μ-2-aminopyrimidine-κ²N¹:N³]

Abstract

In the title supramolecular complex, [Ag(2)Cl(2)(C(4)H(5)N(3))(C(18)H(15)P)(2)](n), a one-dimensional chain is formed by dimeric [Ag(2)Cl(2)(PPh(3))(2)] units bridged by 2-aminopyrimidine moieties. The Ag atoms are four-coordinate, with an AgCl(2)NP core. A crystallographic inversion centre is located in the centre of the Ag(2)Cl(2) chelate ring, while the crystallographic twofold axis bisects the 2-aminopyrimidine ligand.

Synthesis and Photophysical Properties of Emissive Silver(I) Halogenido Coordination Polymers Composed of {Ag2X2} Units Bridged by Pyrazine, Methylpyrazine, and Aminopyrazine

“…In conclusion, we have prepared a series of strongly luminescent silver­(I) halogenido complexes AgX-L (X = I, Br; L = pyz, Mepyz, ampyz). Although a number of [Cu 2 X 2 (PPh 3 ) 2 (μ-L) n ] have been prepared and shown to be strongly emissive, − examples of the corresponding silver­(I) complexes are limited. ,,− The present study shows that AgX-L is a good scaffold for strongly emissive silver complexes. The systematic preparation of isomorphous complexes enables a sufficiently accurate estimation of the energies of the M­(X)-to-L CT ESs of silver complexes from those of their copper congeners.…”

“…The structures of AgX-L and CuBr-L prepared in this study are typical for complexes with the formula [M 2 X 2 (PPh 3 ) 2 (μ-L)] n (M = Cu, Ag; X = I, Br, Cl). − ,, As shown in Tables S4 and S5, the bond distances around the silver atom in the present complexes are in the range of related compounds having Ag 2 X 2 P 2 N 2 geometry (Table S6). ,,− As shown in Tables S5 and S7, whereas the difference between Ag–P av and Cu– P av (0.20 Å) is comparable to the differences between Ag–Br av (2.73 Å) and Cu–Br av (2.54 Å), the difference between Ag–N av and Cu–N av is 0.30 Å, showing that imino ligand L is less favorable for the monovalent silver ion than the phosphine ligand, which can explain the requirement of an excess amount of L in the synthesis of AgX-L . Although various ligands are known to afford [Cu 2 X 2 (PPh 3 ) 2 (L) n ] ( n = 1, 2), − only 4,4′-bipyridine (bpy), 2-aminopyrimidine, , 2-aminopyridine, and pyridine , have been reported to afford [Ag 2 X 2 (PPh 3 ) 2 (L) n ].…”

“… ,,− As shown in Tables S5 and S7, whereas the difference between Ag–P av and Cu– P av (0.20 Å) is comparable to the differences between Ag–Br av (2.73 Å) and Cu–Br av (2.54 Å), the difference between Ag–N av and Cu–N av is 0.30 Å, showing that imino ligand L is less favorable for the monovalent silver ion than the phosphine ligand, which can explain the requirement of an excess amount of L in the synthesis of AgX-L . Although various ligands are known to afford [Cu 2 X 2 (PPh 3 ) 2 (L) n ] ( n = 1, 2), − only 4,4′-bipyridine (bpy), 2-aminopyrimidine, , 2-aminopyridine, and pyridine , have been reported to afford [Ag 2 X 2 (PPh 3 ) 2 (L) n ].…”