Exploring Structure–Property Relationships of Silver 4‐(Phenylethynyl)pyridine Complexes

Abstract

Silver(I) salts demonstrate a strong preference for forming linear complexes when reacted with 4-(phenylethynyl)pyridine (pep). The packing of these complexes was found to be strongly influenced by the counteranions, namely PF 6 -, BF 4 -, NO 2 -, NO 3 -, MeCO 2 -, CF 3 CO 2 -, MeSO 3 -, Tosand SCN -. This study evaluates a family of twelve solid-state structures that exhibit varying metal-to-ligand ratios, [Ag(pep) 2 ][PF 6 ]· MeCN, [Ag(pep) 2 ][PF 6 ], [Ag(pep) 2 ][BF 4 ], [Ag(pep) 2 ][Ag(NO 2 ) 2 ], [Ag(pep) 2 ][NO 3 ]·2H 2 O, [Ag(pep) 2 ][Ag(NO 3 ) 2 ], [Ag(pep) 2 (MeCO 2 )]· [a]

Molecular Motion and Ligand Stacking Influence Thermal Expansion Behavior and Argentophilic Forces in Silver Coordination Complexes

“…One oxygen atom of the p -TolSO 3 counterion coordinates weakly with the silver atom in all coordination complexes at all temperatures (Ag···O distances range from 2.5–2.8 Å). The distance is similar to other reported Ag p -TolSO 3 complexes with pyridine ligands. ,− The complexes [Ag­( p -TolSO 3 )­( PAB ) 2 ], [Ag­( p -TolSO 3 )­( Azo ) 2 ], and [Ag­( p -TolSO 3 )­( Azo ) 2 ]­EtOH exhibit disorder in the sulfonate group. The disorder is present at every temperature for [Ag­( p -TolSO 3 )­( Azo ) 2 ] (both forms) and at 290 K for [Ag­( p -TolSO 3 )­( PAB ) 2 ].…”

“…Slow evaporation of the solution containing Ag p -TolSO 3 and SB afforded concomitant crystallization of two polymorphs (see the Supporting Information, Section 8). A complex of Ag p -TolSO 3 with PAB has been previously reported by crystallization in ethanol or acetonitrile, and the complex contains a free PAB ligand . We obtained a different form here, and all ligands are coordinated to silver atoms.…”

“…A complex of Ag p-TolSO 3 with PAB has been previously reported by crystallization in ethanol or acetonitrile, and the complex contains a free PAB ligand. 22 We obtained a different form here, and all ligands are coordinated to silver atoms. Two crystal forms were obtained by crystallizing Ag p-TolSO 3 and Azo.…”

Iodine(i) complexes incorporating sterically bulky 2-substituted pyridines

“…3) revealed signicantly lengthened Ag-N bond lengths of 2.210(2) and 2.210(2) Å, which are, as best as can be determined, 17 some of the longest known to date for a discrete, linear silver(I) complex incorporating 2substituted pyridines, only rivalled by those of [Ag(4-(phenylethynyl)pyridine) 2 ] + (2.214(5) and 2.217(5) Å). 27 Whilst longer Ag-N bond lengths are present in the literature, in those instances the elongation can be associated to the complexes exhibiting signicantly distorted N-Ag-N angles due to partial coordination from another donor to the silver(I) centre, such as coordination from an anion, 28,29 or from strain caused by the ligand system due to it being dimeric/polymeric in nature, 30 or both. 31 Unlike in 1a and 1b, the pyridyl ligands in 2a are not coplanar, nor do they assume an anti-conguration, with a N-Ag-N angle of 173.04 (7) and an angle of 78.4 between the planes of the two pyridyl rings.…”

Anion···π Interactions and Metastability: Structural Transformations in a Silver–Pyrazine Network

“…Furthermore, by engineering weakly interacting linear coordination‐polymer chains barriers to solid‐state reorganisation such as interpenetration can be suppressed. These ideas were borne out in our previous work with rod‐like linear silver complexes …”