Two Novel One-Dimensional α-Keggin-Based Coordination Polymers with Argentophilic {Ag3}3+/{Ag4}4+ Clusters

This is the authors' abstract. We don't add key points for this paper.

Two novel α-Keggin anion-based coordination polymers with argentophilic {Ag 3 } 3+ /{Ag 4 } 4+ clusters, [{Ag 3 (bpy) 4 }{PMo 12 O 40 }]·2H 2 O ( 1 ), [{Ag(bpy)} 2 {Ag 4 (bpy) 6 }{PMo 11 VO 40 }][{Ag(bpy)} 2 {PMo 11 VO 40 }] ( 2 ), have been hydrothemally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The crystal data for these are the following: C 40 H 36 Ag 3 Mo 12 N 8 O 42 P ( 1 ), triclinic P 1̅, a = 10.5245(19) Å, b = 12.058(2) Å, c = 13.530(2) Å, α = 87.015(2)°, β = 72.146(2)°, γ = 86.563(2)°, Z = 1; C 100 H 80 Ag 8 Mo 22 N 20 O 80 P 2 V 2 ( 2 ), triclinic P 1̅, a = 13.3603(15) Å, b = 16.3035(18) Å, c = 16.7523(19) Å, α = 89.896(2)°, β = 84.000(2)°, γ = 88.066(2)°, Z = 1. Polymer 1 consists of an infinite zigzag one-dimensional (1D) chain constructed from [Ag 3 (bpy) 4 ] 3+ clusters and [PMo 12 O 40 ] 3− anions. Polymer 2 consists of isolated bisupporting [{Ag(bpy)} 2 {PMo 11 VO 40 }] 2− anions and infinite 1D cationic chains [{Ag(bpy)} 2 {Ag 4 (bpy) 6 }{PMo 11 VO 40 }] 2+ constructed from [{Ag(bpy)} 2 {PMo 11 VO 40 }] 2− anions bridged via {Ag 4 (bpy) 6 } 4+ clusters. Argentophilic {Ag 3 } 3+ and {Ag 4 } 4+ interactions exist in polymers 1 and 2 . Ag···Ag interactions were proven using density functional theory, and the luminescent properties were investigated in polymers 1 and 2. The electrochemical behavior of the polymers modified carbon paste electrode ( 1 -CPE, 2 -CPE) and their electrocatalytic reductions of nitrite were investigated. Both 1 -CPE and 2 -CPE show good electrocatalytic activity toward the reduction of the nitrite and remarkable stability that can be ascribed to their insolubility.