Efficient Fe‐Co‐N‐C Electrocatalyst Towards Oxygen Reduction Derived from a Cationic CoII‐based Metal–Organic Framework Modified by Anion‐Exchange with Potassium Ferricyanide

Fe‐Co‐N‐C electrocatalysts have proven superior to their counterparts (e.g. Fe‐N‐C or Co‐N‐C) for the oxygen reduction reaction (ORR). Herein, we report on a unique strategy to prepare Fe‐Co‐N‐C?x (x refers to the pyrolysis temperature) electrocatalysts which involves anion‐exchange of [Fe(CN)₆]^3? into a cationic Co^II‐based metal‐organic framework precursor prior to heat treatment. Fe‐Co‐N‐C‐900 exhibits an optimal ORR catalytic performance in an alkaline electrolyte with an onset potential (E_onset: 0.97 V) and half‐wave potential (E_1/2: 0.86 V) comparable to that of commercial Pt/C (E_onset=1.02 V; E_1/2=0.88 V), which outperforms the corresponding Co‐N‐C‐900 sample (E_onset=0.92 V; E_1/2=0.84 V) derived from the same MOF precursor without anion‐exchange modification. This is the first example of Fe‐Co‐N‐C electrocatalysts fabricated from a cationic Co^II‐based MOF precursor that dopes the Fe element via anion‐exchange, and our current work provides a new entrance towards MOF‐derived transition‐metal (e.g. Fe or Co) and nitrogen‐codoped carbon electrocatalysts with excellent ORR activity.     

Electrocatalysis of Water Oxidation by H2O‐Capped Iridium‐Oxide Nanoparticles Electrodeposited on Spectroscopic Graphite

Electrocatalysis of water oxidation by 1.54 nm IrO_x nanoparticles (NPs) immobilized on spectroscopic graphite electrodes was demonstrated to proceed with a higher efficiency than on all other, hitherto reported, electrode supports. IrO_x NPs were electrodeposited on the graphite surface, and their electrocatalytic activity for water oxidation was correlated with the surface concentrations of different redox states of IrO_x as a function of the deposition time and potential. Under optimal conditions, the overpotential of the reaction was reduced to 0.21 V and the electrocatalytic current density was 43 mA cm^?2 at 1 V versus Ag/AgCl (3 M KCl) and pH 7. These results beneficially compete with previously reported electrocatalytic oxidations of water by IrO_x NPs electrodeposited onto glassy carbon and indium tin oxide electrodes and provide the basis for the further development of efficient IrO_x NP‐based electrocatalysts immobilized on high‐surface‐area carbon electrode materials.     

Ammine(2,2′‐bipyridine‐κ2N,N′)silver(I) nitrate: a dimer formed by π–π stacking and ligand‐unsupported Ag...Ag interactions

Reaction of AgNO₃ and 2,2′‐bipyridine (bipy) under ultrasonic treatment gave the title compound, [Ag(C₁₀H₈N₂)(NH₃)]NO₃. The crystal structure consists of dimers formed by two symmetry‐related Ag^I–bipy monomers connected through intra‐dimer π–π stacking and ligand‐unsupported Ag...Ag interactions. A crystallographic C2 axis passes through the mid‐point of and is perpendicular to the Ag...Agⁱ(−x + 1, y, −z + ) axis. In addition, each Ag^I cation is coordinated by one chelating bipy ligand and one ammine ligand, giving a trigonal coordination environment capped by the symmetry‐equivalent Ag atom. Molecules are assembled by Ag...Ag, π–π, hydrogen‐bond (N—H...O and C—H...O) and weak Ag...π interactions into a three‐dimensional framework. Comparing the products synthesized under different mechanical treatments, we found that reaction conditions have a significant influence on the resulting structures. The luminescence properties of the title compound are also discussed.     

Electrochemical Phase Evolution of Metal‐Based Pre‐Catalysts for High‐Rate Polysulfide Conversion

In situ evolution of electrocatalysts is of paramount importance in defining catalytic reactions. Catalysts for aprotic electrochemistry such as lithium–sulfur (Li‐S) batteries are the cornerstone to enhance intrinsically sluggish reaction kinetics but the true active phases are often controversial. Herein, we reveal the electrochemical phase evolution of metal‐based pre‐catalysts (Co₄N) in working Li‐S batteries that renders highly active electrocatalysts (CoS_x). Electrochemical cycling induces the transformation from single‐crystalline Co₄N to polycrystalline CoS_x that are rich in active sites. This transformation propels all‐phase polysulfide‐involving reactions. Consequently, Co₄N enables stable operation of high‐rate (10 C, 16.7 mA cm^?2) and electrolyte‐starved (4.7 μL mg_S^?1) Li‐S batteries. The general concept of electrochemically induced sulfurization is verified by thermodynamic energetics for most of low‐valence metal compounds.     

Microliter Volume Determination of Cosmetic Mercury with a Partially Crosslinked Poly(4‐vinylpyridine) Modified Screen‐Printed Three‐Electrode Portable Assembly

We successfully demonstrated microliter (μL) volume determination of Mercury (Hg) using an in‐built screen‐printed three electrodes containing partially crosslinked poly(4‐vinlylpyridine) (designated as pcPVP) modified carbon‐working, carbon‐counter, and Ag⁺‐quasireference electrodes (SPE/pcPVP) in a pH 4 acetate buffer solution with 2 M KCl by using the square wave anodic stripping voltammetric (SWASV) technique. Instrumental and solution phase conditions were systematically optimized. Experiments were carried out by simply placing a 500 μL‐droplet of Hg containing real sample mixed with the base electrolyte on the SPE/pcPVP surface. The SPE/Ag⁺ quasi‐reference system shifted the Hg‐SWASV detection potential ca. 250 mV positive, but the quantitative current values were appreciably similar to that of a standard Ag/AgCl reference electrode. Under optimal condition, the calibration graph is linear in the window of 100–1000 ppb of the Hg droplet system with a detection limit of 69.5 ppb (S/N=3). Finally real sample assays were demonstrated for prohibited cosmetic Hg containing skin‐lightening agents in parallel with ICP‐OES measurements.     

Electrochemical Synthesis of Chitosan‐co‐polyaniline/WO3⋅nH2O Composite Electrode for Amperometric Detection of NO2 Gas

An electrode of hydrated tungsten oxide (WO₃?nH₂O) embedded chitosan‐co‐polyaniline (CHIT‐co‐PANI) composite was electrochemically prepared on an indium tin oxide (ITO) coated glass surface using mineral acid as a supporting electrolyte. The resulting CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode was characterized using ultraviolet‐visible spectroscopy (UV‐vis), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and scanning electron microscopy (SEM). The composite electrode exhibited a three‐dimensional nanofibrous structure with the diameter of the nanofibers ranging from 20 to 100 nm. The CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode allowed for the low potential detection of NO₂ gas in acidic medium. The NO₂ gas sensing characteristics were studied by measuring change in the current with respect to concentration and time. Using the CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode, NO₂ gas was detected electrochemically without interference at pH 2.0 and 0.25 V vs. Ag/AgCl. The current of the electrochemical cell with the CHIT‐co‐PANI/WO₃?nH₂O/ITO electrode decreased linearly with an increase in NO₂ gas concentration in a range from 100 to 500 ppb with a response time of eight seconds.     

catena‐Poly[[silver(I)‐μ‐[9,10‐bis(1H‐benzimidazol‐1‐ylmethyl)anthracene]‐κ2N3:N3′] bis(nitrato‐κO)silver(I)]

Yellow needle‐shaped crystals of the title compound, {[Ag(C₃₀H₂₂N₄)][Ag(NO₃)₂]}_n, were obtained by the reaction of AgNO₃ and 9,10‐bis(benzimidazol‐1‐ylmethyl)anthracene (L) in a 2:1 ratio. The asymmetric unit consists of two Ag^I cations, one half L ligand and one nitrate anion. One Ag^I cation occupies a crystallographic inversion centre and links two N‐atom donors of two distinct L ligands to form an infinite one‐dimensional coordination polymer. The second Ag^I cation lies on a crystallographic twofold axis and is coordinated by two O‐atom donors of two nitrate anions to form an [Ag(NO₃)₂]⁻ counter‐ion. The polymeric chains are linked into a supramolecular framework via weak Ag...O [3.124 (5) Å] and Ag...π (2.982 Å) interactions (π is the centroid of an outer anthracene benzene ring). The π interactions contain two short Ag...C contacts [2.727 (6) and 2.765 (6) Å], which can be considered to define Ag–η²‐anthracene bonding interactions. In comparison with a previously reported binuclear Ag^I complex [Du, Hu, Zhang, Zeng & Bu (2008). CrystEngComm, 10 , 1866–1874], this new one‐dimensional coordination polymer was obtained by changing the metal–ligand ratio during the synthesis.     

Core Modulation of 70‐Nuclei Core‐Shell Silver Nanoclusters

The reaction of {(HNEt₃)₂[Ag₁₀(tBuC₆H₄S)₁₂]}_n, Ag₂O, Na₂MoO₄, and m‐methoxybenzoic acid (Hmbc) in CH₃OH/CH₂Cl₂ led to yellow crystals of [Ag₄S₄ (MoO₄)₅@Ag₆₆] (SD/Ag70b; SD=SunDi) only, while in the presence of DMF, additional dark‐red crystals of [Ag₁₀@ (MoO₄)₇@Ag₆₀] (SD/Ag70a) were obtained. SD/Ag70b consists of five MoO₄^2? ions wrapped by a shell of 66 Ag atoms, while SD/Ag70a contains a rare Ag₁₀ kernel consisting of five tetrahedra sharing faces and edges, surrounded by seven MoO₄^2? ions enclosed in a shell of 60 Ag atoms. The formation of the Ag₁₀ kernel originates from a reduction reaction during the self‐assembly process that involves DMF. This work provides the structural information of a unique Ag₁₀ kernel (five fused Ag₄ tetrahedra) and paves an avenue to trap elusive silver species with hierarchical multi‐shell silver nanocluster assemblies with the help of anion templates.     

Powder study of poly[(μ2‐2,2‐dimethylpropane‐1,3‐diyl diisocyanide)‐μ2‐iodido‐silver(I)]

In order to explore the chemistry of the bidentate ligand 2,2‐dimethylpropane‐1,3‐diyl diisocyanide and to investigate the effect of counter‐ions on the polymeric structure of (2,2‐dimethylpropane‐1,3‐diyl diisocyanide)silver(I) complexes, the title polymeric compound, [AgI(C₇H₁₀N₂)]_n, was synthesized by treatment of 2,2‐dimethylpropane‐1,3‐diyl diisocyanide with AgI. X‐ray powder diffraction studies show, as expected, a polymeric structure, similar to the very recently reported Cl⁻ and NO₃⁻ analogues [AgX(C₇H₁₀N₂)]_n (X = Cl⁻ or NO₃⁻). In the title structure, the Ag^I centre is bridged to two adjacent Ag^I neighbours by bidentate 2,2‐dimethylpropane‐1,3‐diyl diisocyanide ligands via the NC groups to form [Ag{CNCH₂C(CH₃)₂CH₂NC}]_n chains. The iodide counter‐ions crosslink the Ag^I centres of the chains to form a two‐dimensional polymeric {[Ag{CNCH₂C(CH₃)₂CH₂NC}]I}_n network. This study also shows that this bidentate ligand forms similar polymeric structures on treatment with AgX, regardless of the nature of the counter‐ion X⁻, and also has a strong tendency to form polymeric complexes rather than dimeric or trimeric ones.     

A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction

Layered two‐dimensional (2D) conjugated metal–organic frameworks (MOFs) represent a family of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures, excellent electrical conductivity, and highly exposed well‐defined molecular active sites. Herein, we report a copper phthalocyanine based 2D conjugated MOF with square‐planar cobalt bis(dihydroxy) complexes (Co‐O₄) as linkages (PcCu‐O₈‐Co) and layer‐stacked structures prepared via solvothermal synthesis. PcCu‐O₈‐Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity (E_1/2=0.83 V vs. RHE, n=3.93, and j_L=5.3 mA cm^?2) in alkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro‐electrochemistry and theoretical modeling as well as contrast catalytic tests, we identified the cobalt nodes as ORR active sites. Furthermore, when employed as a cathode electrocatalyst for zinc–air batteries, PcCu‐O₈‐Co delivers a maximum power density of 94 mW cm^?2, outperforming the state‐of‐the‐art Pt/C electrocatalysts (78.3 mW cm^?2).     

A Flame‐Reaction Method for the Large‐Scale Synthesis of High‐Performance SmxCoy Nanomagnets

We report a flame‐reaction method to synthesize high‐performance Sm_xCo_y (x=1, y=5; x=2, y=17) particles on a multigram scale. This flame reaction allows the controlled decomposition of Sm(NO₃)₃ and Co(NO₃)₂ to 320 nm SmCo‐O (SmCoO₃ + Co₃O₄) particles. A 5.8 g sample of SmCo_3.8‐O particles was coated with CaO and then reduced at 900 °C by Ca to give 4.2 g of 260 nm SmCo₅ particles. The SmCo₅ particles are strongly ferromagnetic and the aligned particles in epoxy resin exhibit a large room‐temperature coercivity (H_c) of 41.8 kOe and giant (BH)_max (maximum magnetic energy product) of 19.6 MGOe, the highest value ever reported for SmCo₅ made by chemical methods. This synthesis can be extended to synthesize Sm₂Co₁₇ particles, providing a general approach to scaling up the synthesis of high‐performance Sm_xCo_y nanomagnets for permanent magnet applications.     

Biomimetic synthesis of the arachidic acid/Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>S nanocomposite films

Ag _x Cd _y S nanoparticles were obtained in arachidic acid (AA) monolayer containing Ag⁺ and Cd²⁺ under H₂S flow. The AA/Ag _x Cd _y S monolayers were deposited onto solid substrate to prepare LB films. The UV-vis spectrum showed that the LB film exhibited notable quantum-size effect. The small-angle X-ray diffraction revealed periodic structure of the LB films. The molar ratio of Ag to Cd in AA/Ag _x Cd _y S film was ca. 1 : 5 as measured by the XPS. TEM and FTIR spectroscopy showed that the head-groups of arachidic acid molecules controlled formation of Ag _x Cd _y S nanoparticles in the monolayer.     

catena‐Poly[[silver(I)‐μ‐1,3‐bis(4‐pyridyl)propane] hemi(naphthalene‐1,5‐disulfonate) dihydrate]: a three‐dimensional metallo‐supramolecular sandwich lamellar network

The title compound, {[Ag(C₁₃H₁₄N₂)](C₁₀H₆O₆S₂)_0.5·2H₂O}_n, (I), features a three‐dimensional supramolecular sandwich architecture that consists of two‐dimensional cationic layers composed of polymeric chains of silver(I) ions and 1,3‐bis(4‐pyridyl)propane (bpp) ligands, linked by Ag...Ag and π–π interactions, alternating with anionic layers in which uncoordinated naphthalene‐1,5‐disulfonate (nds²⁻) anions and solvent water molecules form a hydrogen‐bonded network. The asymmetric unit consists of one Ag^I cation linearly coordinated by N atoms from two bpp ligands, one bpp ligand, one half of an nds²⁻ anion lying on a centre of inversion and two solvent water molecules. The two‐dimensional {[Ag(bpp)]⁺}_n cationic and {[(nds)·2H₂O]²⁻}_n anionic layers are assembled into a three‐dimensional supramolecular framework through long secondary coordination Ag...O interactions between the sulfonate O atoms and Ag^I centres and through nonclassical C—H...O hydrogen bonds.     

catena‐Poly[[disilver(I)(Ag—Ag)‐bis[μ‐1,1′‐(butane‐1,4‐diyl)diimidazole‐κ2N3:N3′]] bis(perchlorate)]: a double helix stabilized by ligand‐unsupported argentophilic interactions

The title compound, {[Ag₂(C₁₀H₁₄N₄)₂](ClO₄)₂}_n, is a one‐dimensional coordination polymer formed by Ag^I atoms linearly bridged by 1,1′‐(butane‐1,4‐diyl)diimidazole molecules. The chains have a helical arrangement and pairs of chains are held together by the rarely reported ligand‐unsupported Ag—Ag interaction [2.966 (1) Å], which results in a double‐helix structure. The double helix contains twisted 24‐membered metallomacrocycles, which are composed of four Ag atoms and two ligands. The Ag atoms lie on twofold axes.     

Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag12}‐in‐{W76} Polyoxometalates under Supramolecular Control

We report the time‐resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one‐pot reaction) of the form: [H_(10+m)Ag₁₈Cl(Te₃W₃₈O₁₃₄)₂]_n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self‐organization of two {Te₃W₃₈} units around a single chloride template and the formation of a {Ag₁₂} cluster, giving a {Ag₁₂}‐in‐{W₇₆} cluster‐in‐cluster in compound 1 , which further aggregates to cluster compounds 2 and 3 by supramolecular Ag‐POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI‐MS. Further, control experiments demonstrate the crucial role that TeO₃^2?, Cl^?, and Ag⁺ play in the self‐assembly of compounds 1 – 3 .     

Anion‐directed Silver(I) Coordination Assemblies Based on 1‐(2‐Pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazolewith Diverse Supramolecular Networks and Dichromate Removal Capabilities

A series of silver(I) supramolecular complexes, namely, {[Ag(L²⁴)](NO₃)}_n ( 1 ), [Ag₂(L²⁴)(NO₂)₂]_n ( 2 ), and {[Ag_1.25(L²⁴)(DMF)](PF₆)_1.25}_n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L²⁴) and silver(I) salts with different anions (AgNO₃, AgNO₂, AgPF₆). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag₂N₄ ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent Ag^I centers are interlinked by L²⁴ ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L²⁴ ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr₂O₇^2–) capture in water system, which can be ascribed to the anion‐exchange.     

Study of the Electrochemical Behavior of Disperse Blue 1‐Modified Graphite Electrodes. Application to the Flow Determination of NADH

The preparation and the electrochemical study of Disperse Blue 1‐chemically modified electrodes (DB1‐CME), as well as their efficiency for the electrocatalytic oxidation of NADH is described. The proposed mediator was immobilized by physical adsorption onto graphite electrodes. The electrochemical behavior of DB1‐CME was studied with cyclic voltammetry. The electrochemical redox reaction of DB1 was found to be reversible, revealing two well‐shaped pair of peaks with formal potentials 152 and ?42 mV, respectively, (vs. Ag/AgCl/3M KCl) at pH 6.5. The current I_p has a linear relationship with the scan rate up to 800 mV s^?1, which is indicative for a fast electron transfer kinetics. The dissociation constants of the immobilized DB1 redox couple were calculated pK₁=4 and pK₂=5. The electrochemical rate constants of the immobilized DB1 were calculated k₁°=18 s^?1 and k₂°=23 s^?1 (Γ=2.36 nmol cm^?2). The modified electrodes were mounted in a flow injection manifold, poised at +150 mV (vs. Ag/AgCl/3M KCl) and a catalytic current due to the oxidation of NADH was measured. The reproducibility was 1.4% RSD (n=11 for 30 μM NADH) The behavior of the sensor towards different reducing compounds was investigated. The sensor exhibited good operational and storage stability.     

A novel three‐dimensional AgI coordination polymer based on mixed naphthalene‐1,5‐disulfonate and aminoacetate ligands

The three‐dimensional coordination polymer poly[[bis(μ₃‐2‐aminoacetato)di‐μ‐aqua‐μ₃‐(naphthalene‐1,5‐disulfonato)‐hexasilver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}_n, based on mixed naphthalene‐1,5‐disulfonate (L1) and 2‐aminoacetate (L2) ligands, contains two Ag^I centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five‐coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one Ag^I cation in a distorted trigonal–bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two Ag^I cations in a slightly octahedral coordination geometry. Ag3 is four‐coordinated by two O atoms from two L2 anions and two Ag^I cations in a slightly distorted square geometry, while Ag4 is also four‐coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one Ag^I cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one‐dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two‐dimensional layer, and the layers are further bridged by L1 anions to generate a novel three‐dimensional framework. Moreover, hydrogen‐bonding interactions consolidate the network.     

Electrochemical Fabrication and Properties of Highly Ordered Fe‐Doped TiO2 Nanotubes

Highly‐ordered Fe‐doped TiO₂ nanotubes (TiO₂nts) were fabricated by anodization of co‐sputtered Ti–Fe thin films in a glycerol electrolyte containing NH₄F. The as‐sputtered Ti–Fe thin films correspond to a solid solution of Ti and Fe according to X‐ray diffraction. The Fe‐doped TiO₂nts were studied in terms of composition, morphology and structure. The characterization included scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, UV/Vis spectroscopy, X‐ray photoelectron spectroscopy and Mott–Schottky analysis. As a result of the Fe doping, an indirect bandgap of 3.0 eV was estimated using Tauc’s plot, and this substantial red‐shift extends its photoresponse to visible light. From the Mott–Schottky analysis, the flat‐band potential (E_fb) and the charge carrier concentration (N_D) were determined to be ?0.95 V vs Ag/AgCl and 5.0 ×10¹⁹ cm^?3 respectively for the Fe‐doped TiO₂nts, whilst for the undoped TiO₂nts, E_fb of ?0.85 V vs Ag/AgCl and N_D of 6.5×10¹⁹ cm^?3 were obtained.     

A stair‐like two‐dimensional silver(I) coordination polymer of N′‐(3‐cyanobenzylidene)nicotinohydrazide

The structure of the title compound, poly[[[μ₃‐N′‐(3‐cyanobenzylidene)nicotinohydrazide]silver(I)] hexafluoroarsenate], {[Ag(C₁₄H₁₀N₄O)](AsF₆)}_n, at 173 K exhibits a novel stair‐like two‐dimensional layer and a three‐dimensional supramolecular framework through C—H...Ag hydrogen bonds. The Ag^I cation is coordinated by three N atoms and one O atom from N′‐(3‐cyanobenzylidene)nicotinohydrazide (L) ligands, resulting in a distorted tetrahedral coordination geometry. The organic ligand acts as a μ₃‐bridging ligand through the pyridyl and carbonitrile N atoms and deviates from planarity in order to adapt to the coordination geometry. Two ligands bridge two Ag^I cations to construct a small 2+2 Ag₂L₂ ring. Four ligands bridge one Ag^I cation from each of four of these small rings to form a large grid. An interesting stair‐like two‐dimensional (3,6)‐net is formed through Ag^I metal centres acting as three‐connection nodes and through L molecules as tri‐linkage spacers.