Chain Coordination Polymer Research Articles

Linking 1D Transition-Metal Coordination Polymers and Different Inorganic Boron Oxides To Construct a Series of 3D Inorganic-Organic Hybrid Borates.

Three inorganic-organic hybrid borates, M(1,4-dab)[B5O7(OH)3] [M = Zn (1), Cd (2), 1,4-dab = 1,4-diaminobutane)] and Co(1,3-dap)[B4O7] (3, 1,3-dap = 1,3-diaminopropane), which integrated characteristics of 1D coordination polymers and 1D/3D inorganic boron oxides have been obtained under solvothermal conditions. Compounds 1 and 2 are isostructural and crystallize in a centrosymmetric space group P21/c; the 3D achiral structures of 1 and 2 consist of the nonhelical Zn/Cd-1,4-dap coordination polymers and 1D B-O chains. Compound 3 crystallizes in a chiral space group P43212; the helical Co-1,3-dap coordination polymer chains are entrained within a 3D B-O network and finally form the chiral framework. Compounds 1-3 represent good examples of using coordination polymers to construct mixed-motif inorganic-organic hybrid borates. Compounds 1 and 2 display blue luminescence when excited with UV light.

Spin-Crossover Iron(II) Coordination Polymer with Fluorescent Properties: Correlation between Emission Properties and Spin State.

A spin-crossover coordination polymer [Fe(L1)(bipy)]n (where L = a N2O22- coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4'-bipyridine) was synthesized and exhibits a 48 K wide thermal hysteresis above room temperature (T1/2↑ = 371 K and T1/2↓ = 323 K) that is stable for several cycles. The spin transition was characterized using magnetic measurements, Mössbauer spectroscopy, and DSC measurements. T-dependent X-ray powder diffraction reveals a structural phase transition coupled with the spin transition phenomenon. The dimeric excerpt {(μ-bipy)[FeL1(MeOH)]2}·2MeOH of the coordination polymer chain crystallizes in the triclinic space group P1̅ and reveals that the packing of the molecules in the crystal is dominated by hydrogen bonds. Investigation of the emission properties of the complexes with regard to temperature shows that the spin crossover can be tracked by monitoring the emission spectra, since the emission color changes from greenish to a yellow color upon the low spin-to-high spin transition.

Probing halogen⋯halogen interactions via thermal expansion analysis

The magnitude of the thermal expansion of the 1-D chain coordination polymer Cu(MeCN)2[AuX2(CN)2] (X = Cl, Br, I) is significantly reduced in the presence of interchain halogen⋯halogen interactions.

Vapour-driven crystal-to-crystal transformation showing an interlocking switch of the coordination polymer chains between 1D and 3D

A rare crystal-to-crystal transformation occurs between 1D coordination polymer chains and 3D mechanically interlocked structures via reversible opening and closing of the homogeneous chains without any change in the coordination mode and composition.

Synthesis and structure of catena((μ2-4,4,10,10-tetramethyl-1,3,7,9-tetraazaspiro[5.5]undecane-2,8-dione-O,O′)dichloro-zinc)

The coordination polymer, catena-((μ2-4,4,10,10-tetramethyl-1,3,7,9-tetraazaspiro[5.5]undecane-2,8-dione-O,O′)dichloro-zinc) {[Zn(C11H20N4O2)Cl2]} n (I), is prepared for the first time from zinc chloride and bicyclic bis(urea), 4,4,10,10-tetramethyl-1,3,7,9-tetraazaspiro[5.5]undecane-2,8-dione, and investigated by X-ray diffraction (CIF file CCDC no. 877812). The crystals of I are monoclinic: space group P21, a = 6.2121(17), b = 11.276(3), c = 11.387(3) A, β = 94.99(3)°, V = 794.6(3) A3, ρ(calcd.) = 1.574 g/cm3, Z = 2. The singe-phase nature of the powder sample of I is confirmed by Rietveld refinement of the powder X-ray diffraction pattern; at 293 K, a = 6.20369(11), b = 11.23336(18), c = 11.36013(16) A, β = 95.3001(11)°, V = 788.28(2) A3. The content of the major phase I in the sample is 100 ± 1%, no impurity lines are found. The zinc coordination polyhedron in the coordination polymer chain is a tetrahedron with vertices being occupied by two chlorine atoms and carbonyl O(1) and O(2) atoms of two TTSU molecules related by the symmetry code (2 − x, 1/2 + y, 2–z). The zinc bond angles are 101.05(12)°–122.13(9)°. The Zn···Zn distance in the polymer is 9.480(2) A. The chains in the coordination polymers are additionally combined by intermolecular hydrogen bonds, N(2)–H(2)···O(2)i (i 2–x, 1/2 + y, 2 − z) (H···O 2.17 A, N−H···O 147°) and N(4)–H(4)···Cl(2)ii (ii 1–x, −1/2 + y, 2–z) (H···Cl 2.48 A, N−H···Cl 159°). The chains are joined into layers along the (0 0 1) plane by intermolecular hydrogen bonds, N(1)−H(1)···Cl(1)iii (iii 1 − x, −1/2 + y, 2–z) (H···Cl 2.78 A, N−H···Cl 148°).

1D π‐d Conjugated Coordination Polymers for Multilevel Memory of Long‐Term and High‐Temperature Stability

Ternary resistive random access memory (RRAM) devices are fabricated from 1D d‐π conjugated coordination polymer chains, which are synthesized via the coordination between Ni(II) salts and benzenetetramine or 3,3′,4,4′‐biphenyltetramine in a solution process. The as‐fabricated devices can retain their memory states for as long as three months at room temperature or work for at least 10 000 s at 150 °C, which is the highest working temperature reported for a ternary RRAM at the time of writing this paper. Thermogravimetric analysis indicates good thermal stability of these two materials because of their good crystallinity and strong intermolecular interaction. The long‐term and high‐temperature stability makes 1D conjugated coordination polymer chains a promising candidate for use as next‐generation material for high‐density data storage via RRAM techniques.

Coordination-Controlled One-Dimensional Molecular Chains in Hexapodal Adenine-Silver Ultrathin Films.

Growth of a silver coordination polymer of a C3-symmetric hexaadenine ligand is studied on highly oriented pyrolytic graphite (HOPG), using high-resolution atomic force microscopy (AFM). This unusual ligand offers 6-fold multidentate coordination sites, and consequently, a multidimensional growth of coordination polymer is expected. Notably, each discrete hexapodal unit is bridged by two silver ions along one of the crystallographic directions, resulting in high interaction energy along this direction. When the polymer was deposited on an HOPG surface from a dilute solution, we observed abundant one-dimensional (1D) coordination polymer chains, with a minimum width of approximately 4.5 nm. The single-crystal structure using X-ray analysis is compared with the surface patterns to reconcile and understand the structure of the 1D polymer on an HOPG surface. The energy levels of Ag-L1 within the proposed model were calculated, on the basis of the X-ray crystal structure, and compared to the ligand states to gain information about the electronic structure of ligand upon Ag coordination. On the basis of the wave functions of a few molecular orbitals (MOs) near the Fermi energy, it is surmised that unfilled MOs may play a crucial role in the transport properties of the Ag-L1 adlayer.

Luminescent cadmium 1,3-adamantanedicarboxylate coordination polymers with diverse topologies depending on dipyridylamide ligands

Hydrothermal reaction of cadmium nitrate, 1,3-adamantanedicarboxylic acid (adcH2), and a hydrogen-bonding capable dipyridylamide ligand afforded five crystalline coordination polymers whose dimensionality depends on the dipyridylamide length and nitrogen donor disposition. The five new phases were structurally characterized via single-crystal X-ray diffraction. [Cd(adc)(4-pmina)]n (1, 4-pmina=4-pyridylmethylisonicotinamide) displays a (4,4) grid topology with [Cd(adc)]n chains pillared by the dipodal dipyridylamide ligands. {[Cd(adc)(4-pmna)(H2O)]·4H2O}n (2, 4-pmna=4-pyridylmethylnicotinamide) displays a similar layered topology, but with octameric water molecule clusters residing in the interlamellar regions. {[Cd(adc)(3-pna)(H2O)]·6H2O}n (3, 3-pna=3-pyridylnicotinamide) possesses 1-D ribbon submotifs due to the syn-conformation and shorter tether length of the dipyridylamide ligands. Compound 3 entrains intriguing “infinite” water molecule tapes comprised of 4- and 5-membered rings. {[Cd2(adc)2(3-pina)2]·H2O}n (4, 3-pina=3-pyridylisonicotinamide) manifests a 4-connected 3D 658cds topology. The minor coordination polymer chain product {[Cd(adc)(3-pyram)2(H2O)]·2H2O}n (5) was isolated along with 4 (3-pyram=3-pyridylamine). Luminescent behavior in 1–4 is attributed to intra-ligand molecular orbital transitions. The new phases were also surveyed for the ability to detect nitrobenzene in ethanol suspension. Thermal decomposition behavior is also discussed herein.

Copper(II) coordination polymers containing neutral trinuclear or anionic dinuclear building units based on pyrazole-3,5-dicarboxylate: Synthesis, structures and magnetic properties

Four novel copper(II) coordination polymers, namely {[Cu3(pzdc)2(pyz)(H2O)6](H2O)}n (1), {[Cu3(pzdc)2(bpy)(H2O)8](H2O)6}n (2), {[Cu4(Hpzdc)2(pzdc)2(bpy)2][Cu(bpy)(H2O)4]n(H2O)4}n (3), and {[Cu3(pzdc)2(ampy)(H2O)5](H2O)3}n (4) (H3pzdc=pyrazole-3,5-dicarboxylic acid, pyz=pyrazine, bpy=4,4′-bipyridine and ampy=2-aminopyrazine) were synthesized and characterized. Compounds 1, 2 and 4 were synthesized by layering method at room temperature while 3 was prepared under solvothermal reaction. Compounds 1 and 2 are one-dimensional (1D) chain coordination polymers, while 3 shows 1D cationic chain coordination polymer with anionic tetranuclear Cu(II) cluster. Compound 4 exhibits 1D ladder-like chain structure. Compounds 1, 2 and 4 consist of neutral trinuclear [Cu3(pzdc)2] building unit which is constructed by μ2-pzdc3− bridging (5-6-5), (6-6-6), and (6-5-5) sequences of Cu(II) geometries for 1, 2 and 4, respectively. Each trinuclear unit is extended via N,N′-linkers giving polymeric chain structure. In contrast, anionic tetranuclear cluster of 3 is built up from two anionic dinuclear metallacyclic [Cu2(Hpzdc)(pzdc)]− building units and double μ2-bpy spacers. The magnetic properties of 1, 2 and 4 exhibit weak antiferromagnetic interactions among Cu(II) centers.

The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-aminophenyl)arsonic acid

(4-Aminophenyl)arsonic acid (p-arsanilic acid) is used as an antihelminth in veterinary applications and was earlier used in the monosodium salt dihydrate form as the antisyphilitic drug atoxyl. Examples of complexes with this acid are rare. The structures of the alkaline earth metal (Mg, Ca, Sr and Ba) complexes with (4-aminophenyl)arsonic acid (p-arsanilic acid) have been determined, viz. hexaaquamagnesium bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate, [Mg(H2O)6](C6H7AsNO3)·4H2O, (I), catena-poly[[[diaquacalcium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ2O:O']-[diaquacalcium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ2O:O]] dihydrate], {[Ca(C6H7AsNO3)2(H2O)2]·2H2O}n, (II), catena-poly[[triaquastrontium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ2O:O']], [Sr(C6H7AsNO3)2(H2O)3]n, (III), and catena-poly[[triaquabarium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ2O:O']], [Ba(C6H7AsNO3)2(H2O)3]n, (IV). In the structure of magnesium salt (I), the centrosymmetric octahedral [Mg(H2O)6]2+ cation, the two hydrogen p-arsanilate anions and the four water molecules of solvation form a three-dimensional network structure through inter-species O-H and N-H hydrogen-bonding interactions with water and arsonate O-atom and amine N-atom acceptors. In one-dimensional coordination polymer (II), the distorted octahedral CaO6 coordination polyhedron comprises two trans-related water molecules and four arsonate O-atom donors from bridging hydrogen arsanilate ligands. One bridging extension is four-membered via a single O atom and the other is eight-membered via O:O'-bridging, both across inversion centres, giving a chain coordination polymer extending along the [100] direction. Extensive hydrogen-bonding involving O-H...O, O-H...N and N-H...O interactions gives an overall three-dimensional structure. The structures of the polymeric Sr and Ba complexes (III) and (IV), respectively, are isotypic and are based on irregular MO7 coordination polyhedra about the M2+ centres, which lie on twofold rotation axes along with one of the coordinated water molecules. The coordination centres are linked through inversion-related arsonate O:O'-bridges, giving eight-membered ring motifs and forming coordination polymeric chains extending along the [100] direction. Inter-chain N-H...O and O-H...O hydrogen-bonding interactions extend the structures into three dimensions and the crystal packing includes π-π ring interactions [minimum ring centroid separations = 3.4666 (17) Å for (III) and 3.4855 (8) Å for (IV)].

The effect of different substituent groups of auxiliary ligands on the photochromic behaviors of bipyridinium-based coordination polymers

Two bipyridinium-based coordination polymers, {[Cd(BCbpy)2(o-BDC)]·13H2O} (1) and {[Cd(BCbpy)2(SA)]·6H2O} (2), have been synthesized and structurally characterized. Single-crystal X-ray diffraction analysis shows that the two compounds have similar one-dimensional coordination polymeric chain structures but different packing patterns. Compound 1 displays fast eye-detectable photochromic behavior while compound 2 is photoinert under 365nm irradiation. The influence of different substituent groups in same site of auxiliary ligands on the photochromic behaviors of the two compounds has been studied in detail.

Synthesis, characterization and antimicrobial activities of triorganotin(IV) complexes with azo-azomethine carboxylate ligands: crystal structure of a tributyltin(IV) and a trimethyltin(IV) complex

Triorganotin(IV) complexes with polyaromatic azo-azomethine carboxylate ligands viz. 2-{4-hydroxy-3-[(2/4-hydroxyphenylimino)methyl]phenylazo}benzoic acids [H3L1/H3L2] were synthesized by reacting the ligands with either bis-tri-n-butyltin(IV) oxide (for 1 and 4) or trimethyltin(IV) chloride in presence of triethylamine (for 2 and 5) or triphenyltin(IV) hydroxide (for 3 and 6). The complexes were characterized by elemental analysis, UV, IR, NMR, and mass spectrometry. NMR spectroscopic studies of the compounds suggested that the complexes adopt four-coordinate tetrahedral geometry around tin in solution. Molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction. Both complexes have distorted trigonal bipyramidal geometry around tin in the solid state. Compound 1 is a one-dimensional (1-D) double chain coordination polymer which can be described as two different 24- and 30-membered non-porous macrocyclic rings constructed from two tributyltin units and two ligand moieties. The structure of 2 comprises a discrete cyclic centrosymmetric dimer with two lattice water molecules per formula unit. In the dimer, two trimethyltin entities are bridged by two ligand moieties. The dimers are further interconnected with lattice water molecules by multiple O–H⋯O hydrogen bonds to form a 1-D H-bonded network. The complexes were also screened for their antimicrobial activities.

Reversible structural transformations between a chain polymer and a metallocage induced by anion templation

A coordination chain polymer, {[Ni(Hdpma)(H2O)4](SO4)3/2·H2O·CH3OH}n (1·H2O·CH3OH, where Hdpma=di(3-pyridylmethyl)ammonium cation), and a tetragonal metallocage, [(SiF62−)⊂{Ni2(Hdpma)4(H2O)2}](SiF6)3·6H2O (2·6H2O), showing anion-directed structure variations have been synthesized through reactants slow diffusion. Anion exchange studies revealed that chain polymer 1 would interconvert to anion-templated metallocage 2 through solution-based anion-induced 1D-to-0D structural transformation, and vice versa, encompassing dissolution, exchange, and recrystallization of structures.

Coordination polymers based on bridging cyanocarbanions and bis-tridentate p-phenylenediamine ligands

Two new Cu(II) coordination polymeric neutral chains of formula [Cu2(1,4-tpbd)(μ-A)2(H2O)2](A)2 with A=tcnoet− (1) and tcnopr− (2) (1,4-tpbd=N,N,N′N′-tetrakis(2-pyridylmethyl)benzene-1,4-diamine, tcnoet−=1,1,3,3-tetracyano-2-ethoxypropenide and tcnopr−=1,1,3,3-tetracyano-2-propoxypropenide) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction and magnetic measurements. 1and2 show alternating chains where the 1,4-tpbd and the cyanocarbanion units (tcnoet− for 1 and tcnopr− for 2) alternate as bridging ligands. The molecular structure can be viewed as [Cu2(μ-tpbd)]4+ dinuclear units (with Cu⋯Cu distances of 8.2233(3) for 1 and 8.2454(7)Å for 2) connected through double cyanocarbanion bridges (Cu(NCCCN)2Cu with Cu⋯Cu distances of 7.4226(6)Å for 1 and 7.4605(3)Å for 2) leading to alternating zig-zag chains running along the [010] direction. Both compounds exhibit a maximum in the thermal variation of the magnetic susceptibility (at ca. 30K in both cases), characteristic of antiferromagnetic exchange interactions occurring mainly through the 1,4-tbpd organic ligand that can be very well reproduced with a S=½ dimer model with g=2.119, J=−35.0cm−1 for 1 and g=2.070 and J=−35.2cm−1 for 2.

Structural Diversity and Magnetic Properties of Seven Coordination Polymers Based on the 2,2′-Phosphinico-dibenzoate Ligand

Seven novel coordination polymers based on 2,2′-phosphinico-dibenzoic acid (H3L), namely, {[Zn3L2(H2O)4]·2H2O}n (1), [Zn3L2(4,4′-bipy)2]n (2), [Zn(HL)(2,2′-bipy)(H2O)]n (3), {[Cd9L6(H2O)8]·4H2O}n (4), [Cd8L4(OH)2(OAc)2(4,4′-bipy)]n (5), [Mn3L2(4,4′-bipy)(EtOH)(H2O)2]n (6), and [Mn(HL)(2,2′-bipy)(H2O)]n (7), were synthesized under hydro(solvo)thermal conditions. These compounds crystallize in the triclinic P1 space group for 1, 4, 5, and 6, the monoclinic space group C2/c for 2, and the monoclinic P21/c space group for 3 and 7. The L3– ligand displays versatile binding modes in 1–7. Compound 1 is a one-dimensional (1-D) chain coordination polymer with a three-dimensional (3-D) supramolecular framework. Compound 2 is a 3-D porous metal–organic framework (MOF) with two different 4,4′-bipyridine linkers. Compounds 3 and 7 show 1-D zigzag chain structures. Compound 4 exhibits a sophisticated 3-D MOF constructed from two types of Cd8 clusters and one Cd2 dimer, which is the first example exhibiting the coexist...

Crystal structure of catena-poly[[aqua-bis-(4-cyano-benzoato-κO)copper(II)]-μ-N,N-di-ethyl-nicotinamide-κ(2) N (1):O

The asymmetric unit of the title polymeric compound, [Cu(C8H4NO2)2(C10H14N2O)(H2O)] n , contains one Cu(II) atom, one coordinating water mol-ecule, two 4-cyano-benzoate (CB) ligands and one coordinating N,N-di-ethyl-nicotinamide (DENA) mol-ecule. The DENA ligand acts as a bis-monodentate ligand, while the CB anions are monodentate. Two O atoms of the CB ligands, one O atom of the water mol-ecule and the pyridine N atom of the DENA ligand form a slightly distorted square-planar arrangement around the Cu(II) atom which is completed to a square-pyramidal coordination by the apically placed O atom of the DENA ligand, with a Cu-O distance of 2.4303 (15) Å. In the two CB anions, the carboxyl-ate groups are twisted relative to the attached benzene rings by 2.19 (12) and 3.87 (15)°, while the benzene rings are oriented at a dihedral angle of 5.52 (8)°. The DENA ligands bridge adjacent Cu(2+) ions, forming polymeric coordination chains running along the b axis. In the crystal, strong water-carboxyl-ate O-H⋯O hydrogen bonds link adjacent chains into layers parallel to (10-1) and weak C-H⋯O hydrogen bonds further stabilize the crystal structure. The cyano group C and N atoms of one of the CB ligands are disordered over two sets of sites with equal occupancies.

Synthesis, structure, luminescence and photocatalytic properties of an uranyl-2,5-pyridinedicarboxylate coordination polymer

An uranium coordination polymer, namely [(UO2(pydc)(H2O)]·H2O (1) (H2pydc=2,5-pyridinedicarboxylic acid), has been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 1D chain coordination polymer, in which UO22+ ions are bridged by 2,5-pyridinedicarboxylate ligands and the chains are connected into a 3D supramolecular network by O–H···O hydrogen bond interactions and π–π stacking interactions. The photocatalytic properties of 1 for degradation of methylene blue (MB), Rhodamine B (RhB) and methyl orange (MO) under Hg-lamp irradiation have been performed, and the amount of the catalyst as well as Hg-lamp irradiation with different power on the photodegradation efficiency of MB have been investigated. Elemental analyses, infrared spectroscopy, TG-DTA analyses and luminescence properties were also discussed.

Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl2(urea)2.

MnCl2(urea)2 is a new linear chain coordination polymer that exhibits slightly counter-rotated Mn2Cl2 rhomboids along the chain-axis. The material crystallizes in the noncentrosymmetric orthorhombic space group Iba2, with each Mn(II) ion equatorially surrounded by four Cl(-) that lead to bibridged ribbons. Urea ligands coordinate via O atoms in the axial positions. Hydrogen bonds of the Cl···H-N and O···H-N type link the chains into a quasi-3D network. Magnetic susceptibility data reveal a broad maximum at 9 K that is consistent with short-range magnetic order. Pulsed-field magnetization measurements conducted at 0.6 K show that a fully polarized magnetic state is achieved at Bsat = 19.6 T with another field-induced phase transition occurring at 2.8 T. Zero-field neutron diffraction studies made on a powdered sample of MnCl2(urea)2 reveal that long-range magnetic order occurs below TN = 3.2(1) K. Additional Bragg peaks due to antiferromagnetic (AFM) ordering can be indexed according to the Ib'a2' magnetic space group and propagation vector τ = [0, 0, 0]. Rietveld profile analysis of these data revealed a Néel-type collinear ordering of Mn(II) ions with an ordered magnetic moment of 4.06(6) μB (5 μB is expected for isotropic S = (5)/2) oriented along the b-axis, i.e., perpendicular to the chain-axis that runs along the c-direction. Owing to the potential for spatial exchange anisotropy and the pitfalls in modeling bulk magnetic data, we analyzed inelastic neutron scattering data to retrieve the exchange constants: Jc = 2.22 K (intrachain), Ja = -0.10 K (interchain), and D = -0.14 K with J > 0 assigned to AFM coupling. This J configuration is most unusual and contrasts the more commonly observed AFM interchain coupling of 1D chains.

High-Nuclearity Silver Thiolate Clusters Constructed with Phosphonates

The n-butylphosphonate ligand has been employed to construct three new silver(I) thiolate compounds. Single-crystal X-ray analysis revealed that complexes 1 and 2 are Ag48 and Ag51 coordination chain polymers, while 3 contains a discrete Ag48 cluster, in which three different kinds of silver(I) thiolate cluster shells enclose three different phosphonate-functionalized silver(I) cluster cores, respectively. The structures of clusters in 1–3 feature three three-shell arrangements, S@Ag12@(nBuPO3)9@Ag36S23, S@Ag11@(nBuPO3)7(MoO4)2 @Ag40S27 and MoO4@Ag12@(nBuPO3)8S6 @Ag36S24, respectively.

High-Nuclearity Silver Thiolate Clusters Constructed with Phosphonates.

The n-butylphosphonate ligand has been employed to construct three new silver(I) thiolate compounds. Single-crystal X-ray analysis revealed that complexes 1 and 2 are Ag48 and Ag51 coordination chain polymers, while 3 contains a discrete Ag48 cluster, in which three different kinds of silver(I) thiolate cluster shells enclose three different phosphonate-functionalized silver(I) cluster cores, respectively. The structures of clusters in 1-3 feature three three-shell arrangements, S@Ag12 @(nBuPO3 )9 @Ag36 S23 , S@Ag11 @(nBuPO3 )7 (MoO4 )2 @Ag40 S27 and MoO4 @Ag12 @(nBuPO3 )8 S6 @Ag36 S24 , respectively.