Intramolecular Ag Research Articles

Intramolecular Folding of PolyT Oligonucleotides Induced by Cooperative Binding of Silver(I) Ions.

Ag+-bridged T-Ag+-T was recently discovered in a Ag+-DNA nanowire crystal, but it was reported that Ag+ had little to no affinity to T nucleobases and T-rich oligonucleotides in solution. Therefore, the binding mode for the formation of this type of novel metallo base pair in solution is elusive. Herein, we demonstrate that Ag+ can interact with polyT oligonucleotides once the concentration of Ag+ in solution exceeds a threshold value. The threshold value is independent of the concentration of the polyT oligonucleotide but is inversely proportional to the length of the polyT oligonucleotide. The polyT oligonucleotides are intramolecularly folded due to their positively cooperative formation and the stack of T-Ag+-T base pairs, resulting in the 5'- and 3'-ends being in close proximity to each other. The intramolecular Ag+-folded polyT oligonucleotide has a higher thermal stability than the duplex and can be reversibly modulated by cysteine.

Silver Ion-Induced Formation of Unprecedented Thorium Nonamer Clusters via Lacuna-Construction Strategy

Silver Ion-Induced Formation of Unprecedented Thorium Nonamer Clusters via Lacuna-Construction Strategy

Backbone thioamide directed macrocyclisation: lactam stapling of peptides.

A novel method for lactam stapling of Asp/Lys-containing peptides has been developed that does not require coupling agents. A backbone thioamide is incorporated at the N-terminal side of the aspartate residue. Ag(I)-promoted activation of the thioamide in the vicinity of the Asp carboxylate generates a cyclic isoimide intermediate that is trapped by the Lys amine to generate the macrolactam. This method is suitable for generation of i,i+2, i,i+3, and i,i+4-spaced lactam-bridged peptides.

Binuclear silver(I) complexes with the non-steroidal anti-inflammatory drug tolfenamic acid: Synthesis, characterization, cytotoxic activity and evaluation of cellular mechanism of action

In this study, two new binuclear silver(I)-tolfenamic acid complexes including picoline derivative ligands, [Ag2(μ-tolf)2(2-pic)2] 1and [Ag2(μ-tolf)2(4-pic)2] 2, were synthesized and identified by elemental analysis, FT-IR, 1H NMR and thermal analysis techniques. The in vitro cytotoxicity of the complexes was investigated against human breast cancer cell lines by XTT, flow cytometry, enzyme activity and western blot studies. The structures of 1 and 2 were clarified by single-crystal X-ray diffraction determination. The data clearly indicated that the Ag(I) ion is coordinated to one auxiliary ligand (2-pic or 4-pic), two tolfenamato ligands and another Ag(I) ion, demonstrating a distorted tetrahedral geometry. The tolfenamato ligands act as a bridging bidentate ligands. The chains are stabilized by intramolecular Ag(I)⋯π and π···π interactions. The 1H NMR and thermal analyses displayed the presence of picoline and tolfenamato ligands in the coordination sphere and the purity of the complexes. Both complexes exhibited potent cytotoxicity against cancer cell lines with higher selectivity than carboplatin. Flow cytometry and enzyme activity studies indicated that both complexes caused an increase in apoptosis, ROS and NO levels, cell cycle arrest, mitochondrial membrane damage and caspase activity, as well as inhibiting PI3K/Akt phosphorylation and modulating the oxidant/antioxidant balance system. Western blot analyses revealed the up-regulation of bax, caspase-3, caspase-9 and p53 proteins, but the down-regulation of bcl-2. These results demonstrate the vigorous apoptotic potential of the novel Ag(I) complexes in human breast cancer MDA-MB-453 cells.

Synthesis and Structural Characterization of a Silver(I) Pyrazolato Coordination Polymer.

Coinage metal(I)···metal(I) interactions are widely of interest in fields such as supramolecular assembly and unique luminescent properties, etc. Only two types of polynuclear silver(I) pyrazolato complexes have been reported, however, and no detailed spectroscopic characterizations have been reported. An unexpected synthetic method yielded a polynuclear silver(I) complex [Ag(μ-L1Clpz)]n (L1Clpz− = 4-chloride-3,5-diisopropyl-1-pyrazolate anion) by the reaction of {[Ag(μ-L1Clpz)]3}2 with (nBu4N)[Ag(CN)2]. The obtained structure was compared with the known hexanuclear silver(I) complex {[Ag(μ-L1Clpz)]3}2. The Ag···Ag distances in [Ag(μ-L1Clpz)]n are slightly shorter than twice Bondi’s van der Waals radius, indicating some Ag···Ag argentophilic interactions. Two Ag–N distances in [Ag(μ-L1Clpz)]n were found: 2.0760(13) and 2.0716(13) Å, and their N–Ag–N bond angles of 180.00(7)° and 179.83(5)° indicate that each silver(I) ion is coordinated by two pyrazolyl nitrogen atoms with an almost linear coordination. Every five pyrazoles point in the same direction to form a 1-D zig-zag structure. Some spectroscopic properties of [Ag(μ-L1Clpz)]n in the solid-state are different from those of {[Ag(μ-L1Clpz)]3}2 (especially in the absorption and emission spectra), presumably attributable to this zig-zag structure having longer but differently arranged intramolecular Ag···Ag interactions of 3.39171(17) Å. This result clearly demonstrates the different physicochemical properties in the solid-state between 1-D coordination polymer and metalacyclic trinuclear (hexanuclear) or tetranuclear silver(I) pyrazolate complexes.

Dinuclear Silver(I) Nitrate Complexes with Bridging Bisphosphinomethanes: Argentophilicity and Luminescence

Two silver nitrate complexes with bisphosphines were obtained and characterized: [Ag(dcypm)]2(NO3)2 (1; dcypm = bis(dicyclohexylphosphino)methane) and [Ag(dppm)]2(Me2PzH)n(NO3)2 (n = 1, 2a; n = 2, 2b; dppm = bis(diphenylphosphino)methane, Me2PzH = 3,5-dimethylpyrazole). The steric repulsions of bulky cyclohexyl substituents prevent additional ligand coordination to the silver atoms in 1. Compounds obtained feature the bimetallic eight-member cyclic core [AgPCP]2. The intramolecular argenthophilic interaction (d(Ag···Ag) = 2.981 Å) was observed in complex 1. In contrast, the coordination of pyrazole led to the elongation of Ag···Ag distance to 3.218(1) Å in 2a and 3.520 Å in 2b. Complexes 1 and 2a possess phosphorescence both in the solution and solid state. Time-dependent density-functional theory (TD-DFT) calculations demonstrate the origin of their different emission profile. In the case of 1, upon excitation, the electron leaves the Ag–P bonding orbital and locates on the intramolecular Ag···Ag bond (metal-centered character). Complex 2a at room temperature exhibits a phosphorescence originating from the 3(M + LP+N)LPhCT state. At 77 K, the photoluminescence spectrum of complex 2a shows two bands of two different characters: 3(M + LP+N)LPhCT and 3LCPh transitions. The contribution of Ag atoms to the excited state in both complexes 2a and 2b decreased relative to 1 in agreement with the structural changes caused by pyrazole coordination.

Regium Bonds between Silver(I) Pyrazolates Dinuclear Complexes and Lewis Bases (N2, OH2, NCH, SH2, NH3, PH3, CO and CNH)

A theoretical study and Cambridge Structural Database (CSD) search of dinuclear Ag(I) pyrazolates interactions with Lewis bases were carried out and the effect of the substituents and ligands on the structure and on the aromaticity were analyzed. A relationship between the intramolecular Ag–Ag distance and stability was found in the unsubstituted system, which indicates a destabilization at longer distances compensated by ligands upon complexation. It was also observed that the asymmetrical interaction with phosphines as ligands increases the Ag–Ag distance. This increase is dramatically higher when two simultaneous PH3 ligands are taken into account. The calculated 109Ag chemical shielding shows variation up to 1200 ppm due to the complexation. Calculations showed that six-membered rings possessed non-aromatic character while pyrazole rings do not change their aromatic character significantly upon complexation.

Luminescent AgI Complexes with 2,2′‐Bipyridine Derivatives Featuring [Ag‐(CF3)2Pyrazolate]4 Units

The tetranuclear silver(I) 3,5‐bis(trifluoromethyl)pyrazolate adducts with 2,2′‐bipyridine derivatives were prepared by the reaction of trinuclear metal complex with the diimines. It was shown that the product structure depends on the reagents ratio: mono‐ and bisdiimine complexes were synthesized. Compounds obtained possess green phosphorescence in the solid state. The short intramolecular Ag···Ag distances (≤ 3 Å) make possible electronic communication between the metal atoms which leads to the dual emissive behavior mainly due to the 3LC phosphorescence with the impact of 3MLCT. The behavior observed was rationalized by the TD‐DFT study.

7-Methyl-6-furylpurine forms dinuclear metal complexes with N3,N9 coordination

Abstract Two dinuclear metal complexes bearing the purine derivative 7-methyl-6-furylpurine (1b) as a ligand are reported. In [Ag2(1b)2(DMSO)2](ClO4)2·DMSO and [Cu2(1b)2(NO3)2], two bridging purine derivatives coordinate the two metal ions via their N3 and N9 positions. In the silver(I) complex, the coordination environment of each metal ion is completed by a DMSO ligand, whereas an additional nitrato ligand coordinates to each copper(I) ion. The intramolecular Ag···Ag distance of 3.1069(5) Å is in agreement with the presence of a weak argentophilic interaction, whereas the Cu···Cu distance of 2.9382(4) Å is too long to be indicative of a cuprophilic interaction. The compounds represent the first examples of dinuclear complexes comprising two N3,N9-bridging purine derivatives without any additional bridging ligand.

A dinuclear silver(I)-mediated base pair in DNA formed from 1, N 6 -ethenoadenine and thymine

The artificial nucleobase 1,N6-ethenoadenine (εA) is shown to form a dinuclear Ag(I)-mediated base pair with a complementary thymine (T) residue in double-helical DNA. The stabilizing effect brought about by the formation of such a metal-mediated base pair amounts to 5–6 °C. It does not depend on the orientation of the base pair within the duplex, i.e. the εA–Ag(I)2–T base pair confers the same stability as the T–Ag(I)2–εA base pair. Circular dichroism studies and temperature-dependent UV spectroscopy were applied to establish the formation of this Ag(I)-mediated base pair. Based on DFT calculations, a base pair configuration is proposed in which one Ag(I) ion is coordinated by εA-N6 and T-O4, whereas the other Ag(I) ion forms coordinate bonds to εA-N7 and T-N3. The computations indicate a short intramolecular Ag⋯Ag contact of 2.87 Å, suggesting that argentophilic interactions may be involved.

Crystal structure of an unknown tetra-hydro-furan solvate of tetra-kis-(μ 3-cyanato-κ(3) N:N:N)tetra-kis-[(triphenyl-phosphane-κP)-silver(I)

In the title compound, [{[(C6H5)3P]Ag}4{NCO}4], a distorted Ag4N4-heterocubane core is set up by four Ag(I) ions being coordinated by the N atoms of the cyanato anions in a μ 3-bridging mode. In addition, a tri-phenyl-phosphine ligand is datively bonded to each of the Ag(I) ions. Intra-molecular Ag⋯Ag distances as short as 3.133 (9) Å suggest the presence of argentophilic (d (10)⋯d (10)) inter-actions. Five moderate-to-weak C-H⋯O hydrogen-bonding inter-actions are observed in the crystal structure, spanning a three-dimensional network. A region of electron density was treated with the SQUEEZE procedure in PLATON [Spek (2015). Acta Cryst. C71, 9-18] following unsuccessful attempts to model it as being part of disordered tetra-hydro-furan solvent mol-ecules. The given chemical formula and other crystal data do not take into account these solvent mol-ecules.

Crystal structure of cyclo-bis-(μ4-2,2-di-allyl-malonato-κ(6) O (1),O (3):O (3):O (1'),O (3'):O (1'))tetra-kis-(triphenyl-phosphane-κP)tetra-silver(I).

In the tetra-nuclear mol-ecule of the title compound, [Ag4(C9H10O4)2(C18H15P)4], the Ag(I) ion is coordinated by one P and three O atoms in a considerably distorted tetra-hedral environment. The two 2,2-di-allyl-malonate anions bridge four Ag(I) ions in a μ4-(κ(6) O (1),O (3):O (3):O (1'),O (3'):O (1')) mode, setting up an Ag4O8P4 core (point group symmetry -4..) of corner-sharing tetra-hedra. The shortest intra-molecular Ag⋯Ag distance of 3.9510 (3) Å reveals that no direct d (10)⋯d (10) inter-actions are present. Four weak intra-molecular C-H⋯O hydrogen bonds are observed in the crystal structure of the title compound, which most likely stabilize the tetra-nuclear silver core.

Silver Salt of 4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine – Characterization of this Primary Explosive

AbstractA new primary explosive, the silver salt of 4,6‐diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine (AgDANT), was synthesized and characterized. AgDANT was prepared with a 97 % yield and characterized by IR spectroscopy, single‐crystal X‐ray diffraction, and DTA. The crystal density of AgDANT is 2.530 g cm−3 and the molecule consists of a centro‐symmetric dimer with a high degree of planarity. The intramolecular AgAg distance is relatively low (331 pm) and can be considered as a strong argentophilic interaction. AgDANT is non‐hygroscopic and its solubility in water (1.27 mg in 100 mL at 23 °C) is on a similar level of solubility to that of silver azide. The sensitivity of AgDANT to impact is slightly higher than that for MF, sensitivity to friction is the same as for LA, and sensitivity to electric discharge is between that for LS and MF. Initiation efficiency of AgDANT was tested in electric detonators and compared to dextrinated lead azide (initiation efficiency of AgDANT is 40 mg for PETN secondary charge). The thermal resistance of detonators with AgDANT is satisfactory; all detonators were fully functional after exposure at 65 °C (30 d) and 85 °C (2 d).

Argentivorous Molecules: Structural Evidence for Ag+–π Interactions in Solution

Tetra-armed cyclens bearing aromatic side arms were prepared by the reductive amination of cyclen with substituted benzaldehydes. When equimolar amounts of Ag(+) ions were added to the ligands, the aromatic rings covered the Ag(+) ions incorporated in the ligand cavities, as if the aromatic ring "petals" caught the Ag(+) ions in the way an insectivorous plant (Venus flytrap) catches insects. The ligands are called "argentivorous molecules". Evidence of intramolecular Ag(+)-π interactions in solution and in the solid state is reported.

Bis[μ2-bis(diphenylphosphanyl)methane-κ2P:P′]bis(μ4-diphenylphosphinato-κ4O:O:O′:O′)bis[μ2-trifluoromethanesulfonato(0.546/0.454)]-κ2O:O′;κ2O:O-tetrasilver(I) acetonitrile disolvate

In the centrosymmetric tetra­nuclear title compound, [Ag4(C12H10O2P)2(CF3O3S)2(C25H22P2)2]·2CH3CN, the AgI atom is coordinated by one P atom from a bis­(diphenyl­phosphan­yl)methane (dppm) ligand, two O atoms from two diphenyl­phosphinate (dpp) ligands and one O atom from a trifluoro­methane­sulfonate (OTf) anion in a highly distorted tetra­hedral geometry. Four AgI atoms are bridged by two dppm ligands, two dpp ligands and two OTf anions, forming a tetra­nuclear complex. An weak intra­molecular Ag⋯Ag [3.2692 (14) Å] inter­action is observed. The OTf anion and one of the phenyl groups in the dppm ligand are disordered over two sets of positions in a 0.546 (4):0.454 (4) ratio. The 0.546-occupied OTf is bonded to two Ag atoms in a μ-(κ2 O:O′) mode, while the 0.454-occupied OTf is bonded in a μ-(κ2 O:O) mode. The methyl group of the acetonitrile solvent mol­ecule is also disordered over two positions with equal occupancy factors.

A linear chain polymer {Ag2[S2P(OC2H5)2]2(bix)} n with multiple emission and red luminescence

The linear chain {Ag2[S2P(OC2H5)2]2(bix)} n 1 was obtained from reaction of Ag[S2P(OC2H5)2] with bix (bix = 1,4-bis(imidazole-l-ylmethyl)benzene). Compound 1 consists of a dinuclear module with intramolecular Ag ··· Ag interactions (2.9842(5) Å). This interaction shows a profound influence on the observed multiple luminescence emissions for 1. Crystal data for 1 at 293(2) K: Space group P 1, a = 9.7158(1), b = 9.8273(2), c = 10.0758(2) Å, α = 70.989(1), β = 89.308(1), γ = 63.868(1)°, V = 806.75(2) Å3, Z = 1, R 1 = 0.0294.

Gold(I) and Silver(I) Mixed-Metal Trinuclear Complexes: Dimeric Products from the Reaction of Gold(I) Carbeniates or Benzylimidazolates with Silver(I) 3,5-Diphenylpyrazolate

Trinuclear mixed-metal gold-silver compounds are obtained by the reaction of gold(I) carbeniate [Au(mu-C(OEt)=NC6H4-p-CH3)]3, TR(carb), or gold(I) imidazolate [Au-mu-C,N-1-benzyl-2-imidazolate]3, TR(bzim), with silver(I) pyrazolate [Ag(mu-3,5-Ph2pz)]3. The crystalline products are mixed-ligand, mixed-metal dimeric products [Au(carb)Ag2(mu-3,5-Ph2pz)2], [Au2(carb)2Ag(mu-3,5-Ph2pz)].CH2Cl2, [Au(bzim)2Ag2(mu-3,5-Ph2pz)], and [Au2(bzim)2Ag(mu-3,5-Ph2pz)]. They have been characterized by elemental analysis and 1H NMR and mass spectrometry. The X-ray structure of [Au(carb)Ag2(mu-3,5-Ph2pz)2] shows it to be a dimer with two Ag...Au contacts between the trinuclear units of 3.083(2) and 3.310(2) A and with average intramolecular Ag...Ag and Au...Ag distances of approximately 3.3 and 3.2 A, respectively. The structure of [Au2(carb)2Ag(mu-3,5-Ph2pz)].CH2Cl2 is a dimer with one intermolecular Au...Au attraction of 3.3354(10) A and a short Ag...Au distance of approximately 3.42 A and intramolecular Ag...Au and Au...Au contacts of approximately 3.2 and approximately 3.3 A, respectively. Packing diagrams of both complexes show that the dimeric units are independent, similar to their parent molecules. The dimers of trinuclear [Au(carb)Ag2(mu-3,5-Ph2pz)2] and [Au2(carb)2Ag(mu-3,5-Ph2pz)].CH2Cl2 crystallize in the triclinic space group P (Z = 2), a = 9.688(3) A, b = 15.542(4) A, c = 23.689(6) A, alpha = 82.560(5) degrees , beta = 87.887(6) degrees , gamma = 78.060(5) degrees , and the orthorhombic space group Pca2(1) (Z = 4), a = 29.644(4) A, b = 7.4582(10) A, c = 30.473(4) A, respectively. The structure of [Au(bzim)Ag2(mu-3,5-Ph2pz)2] is a dimer with two metallophilic Ag...Au interactions of 3.14 A. The complex crystallizes in the monoclinic space group C2/c (Z = 4), a = 26.368(5) A, b = 15.672(3) A, c = 17.010(3) A, beta = 102.206(3) degrees .

Silver(I) Complexes in Coordination Supramolecular System with Bulky Acridine-Based Ligands: Syntheses, Crystal Structures, and Theoretical Investigations on C−H···Ag Close Interaction

In our efforts to investigate the coordination architectures of transition metals and organic ligands with tailored structures, we have prepared two structurally related rigid bulky acridine-based ligands, 9-[3-(2-pyridyl)pyrazol-1-yl]- acridine (L(1)) and 9-(1-imidazolyl)acridine (L2), and synthesized and characterized four of their Ag(I) complexes, {[AgL1](ClO4)}2 (1), {[AgL1](NO3)}2 (2), [AgL2(2)](ClO4) (3), and {[(Ag3L2(3))(NO3)](NO3)2(H2O)}(infinity) (4). The single-crystal X-ray diffraction analysis shows that the structures of 1 and 2 are similar to each other, with the two intramolecular Ag(I) centers of each complex being encircled by two L1 ligands; this forms a unique boxlike cyclic dimer, which is further linked to form one-dimensional (1D) chains of 1 and a two-dimensional (2D) network of 2 by intermolecular face-to-face pi...pi stacking and/or weak C-H...O hydrogen-bonding interactions, respectively. 3 has a mononuclear structure, which is further assembled into a 2D network via intermolecular Ag...O and pi...pi stacking weak interactions. 4 possesses two different 1D motifs that are further interlinked through interlayer face-to-face pi...pi stacking and Ag...O weak interactions, resulting in a 2D network. It is worth noting that one of the interesting structural features of 1, 2, and 4 is the presence of obvious C-H...M hydrogen-bonding interactions between the Ag centers and some acridine ring H atoms identified by X-ray diffraction on the basis of the van der Waals radii. Furthermore, as a representative example, full geometry optimization on the basis of the experimental structure, the natural bond orbital (NBO), and topological analysis of 1 were carried out by DFT and AIM (Atoms in Molecules) calculations. The total C-H...Ag interaction energy in 1 is estimated to be about 14 kJ/mol. Therefore, this work offers three new rare examples (1, 2, and 4) that exhibit C-H...Ag weak interactions, in which the N donors of the acridine rings coordinate to Ag(I) ions. Also, these results strongly support the existence of C-H...Ag close interactions and allow us to have a better understanding of the nature of such interactions in the coordination supramolecular systems.

Metal complexes from 1,1′-di(pyrazinyl)ferrocene: coordination polymers and bridged diferrocenes

Ferrocene-based ligands 1,1'-di(pyrazinyl)ferrocene (L1) and 1,1'-di(2-pyrimidinyl)ferrocene (L2) were synthesized and copper and silver complexes were obtained from L1. Coordination polymers [{Cu(2)(PhCOO)(4)}(L1)](n) (1), [{Cu(2)(C(5)H(11)COO)(4)}(L1)](n) (2), and [{Cu(2)(OAc)(4)}(L1)](n).0.5n[Cu(2)(OAc)(4)(H(2)O)(2)].1.5nCH(3)CN (3) resulted from the reaction with the corresponding copper carboxylates. In all three complexes, L1 links the dinuclear copper carboxylate units to form one-dimensional step-like chains. In 2, these chains are further linked by [Cu(2)(OAc)(4)(H(2)O)(2)] dinuclear units via hydrogen bonding to form sheet structures. The reaction of L1 with copper(I) iodide resulted in a multinuclear complex [(CuI)(4)(L1)(2)].(L1) (4), which contains a [(CuI)(4)(L1)(2)] diferrocene unit with a step-like (CuI)(4) core. Reactions of L1 with silver(I) salts resulted in silver-bridged diferrocenes [Ag(2)(L1)(2)]X(2) (X = ClO(4) (5a, b), NO(3) (6a-c) and PF(6) (7)), some of which incorporate aromatic solvents into their crystal lattices. The intramolecular Ag...Ag separations in these metallamacrocycles (3.211-3.430 A) depended upon the counter-anions and on the coordination mode of the silver ions. In all of these coordination complexes, L1adopts a synperiplanar eclipsed conformation and acts as a bidentate ligand, with only the 5-nitrogen of each pyrazine ring involved in coordination.

Formation of novel discrete silver(i) coordination architectures with quinoline-based monothioethers: adjusting the intramolecular Ag⋯Ag distances and complex structures by ligands modifications and variations of counter anions

In our efforts to design discrete polynuclear metal complexes with tailored structures, four structurally related quinoline-based new monothioether ligands, 8-(2-pyridylsulfanylmethyl)quinoline (L1), 8-(4-pyridyl- sulfanylmethyl)quinoline (L2), 8-(2-pyrimidylsulfanylmethyl)quinoline (L3), 5-methyl-2-(8-quinolylmethyl- sulfanyl)-1,3,4-thiadiazole (L4) have been designed, and six new AgI complexes with these ligands, {[AgL1](ClO4)(CHCl3)}21, [Ag2L1(NO3)2]22, {[AgL1(CH3CN)](PF6)}23, [AgL2(NO3)]24, {[AgL3(CH3OH)](ClO4)}25 and {[AgL4](ClO4)}26 have been synthesized and characterized by single-crystal X-ray diffraction analysis. All six complexes adopt discrete structures, with 1,3,4,5 and 6 being dinuclear and 2 being tetranuclear, and Ag–Ag interactions were found to exist in complexes 1,2,3 and 6, as well as π–π stacking in 1–4. Furthermore, the Ag⋯Ag distances in 1–6 were compared. In the six complexes, the sulfur atoms of the ligands adopt quite different coordination modes: bridging in 1,2 and 3, chelating in 5 and non-coordination in 4 and 6. In addition, the structural differences of 1,2 and 3 indicate that the change in the counter anion greatly influences the coordination modes of the ligands and the coordination geometries of AgI ion, which consequently affects the resulting frameworks of such complexes.