Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C6F5)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study

Six pentafluorophenylplatinum(II) complexes containing proton acceptor atoms (F) and pyridine-like aromatic ligands able to act as proton donors have been synthesized and characterized, with emphasis on the factors that mediate their supramolecular aggregation in the solid state--hydrogen bonds and pi-pi interactions. The crystal structure analyses of the mononuclear complexes cis-[Pt(C6F5)2(napy)](1), cis-[Pt(C6F5)2(CH2napy)](3), cis-[Pt(C6F5)2(2-ammpy)](5), and cis-[Pt(C6F5)2(2-bipym)](6) reveal the influence of D-HPt and D-HF (D=C, N) hydrogen bonding on the organization of molecules into stacks, which can be further interconnected to generate channels. The prevalence of hydrogen bonding over pi-pi interactions between aromatic rings in establishing the nature of the observed supramolecular aggregation is demonstrated.     

Novel supramolecular architectures in group 13 perfluoroaryl complexes. Synthesis and structures of [AlMe(C6F5)(mu-Me)]2 and GaMe(C6F5)2

Novel supramolecular architectures are observed in the solid state structures of [AlMe(C6F5)(mu-Me)]2 (1) and Ga(C6F5)2Me (2) via pi-pi stacking between C6F5 rings and intermolecular aryl-F-->Ga interactions, respectively.     

Unsupported gold(I)-copper(I) interactions through eta1 Au-[Au(C6F5)2]- coordination to Cu+ Lewis acid sites

The reaction of the complex [Au2Ag2(C6F5)4)N[triple bond]CCH3)2]n (1) with 1 equiv of CuCl in the presence of 1 equiv of pyrimidine ligand leads to the formation of the heteronuclear Au(I)-Cu(I) organometallic polymer [Cu{Au(C6F5)2}(N[triple bond]CCH3)(mu2-C4H4N2)]n (2) through a transmetalation reaction. Complex 2 displays unprecedented unsupported Au(I)...Cu(I) interactions of [Au(C6F5)2]- units with the acid Cu(I) sites in a [Cu(N[triple bond]CCH3)(mu2-pyrimidine)]n+(n) polymeric chain. Complex 2 has a rich photophysics in solution and in the solid state.     

1-D Open-channeled 3-D Supramolecular Frameworks Built with 2,3-Dihydroxybutanedioic Acid (H4dhbd) and 2,2':6,2"-Terpyridine (tpy)

The complex [Cu2(H2dhbd)2(tpy)2]·CH3OH·4H2O1 (H4dhbd=2,3-dihydroxybutane-dioic acid, tpy=2,2":6',2"-terpyddine) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space groups P1 with a=8.6859(17), b=11.223(2), c=12.275(2)A,α=112.454(3), β=98.435(3),γ=105.593(3)°, V=1022.5(3) A3, Z=1, C38H42Cu2N6.O18, Mr=997.86, Dc=1.621 g/cm3,μ=1.127 mm-1, F(000)=514, T=293(2) K, the final R=0.0539 and wR=0.1394 for 3550 observed reflections with 1 >20(1). In the dinuclear unit, two CuⅡ atoms are bridged by two H2dhbd chelate anions, forming a 14-membered ring, in which the distance of Cu…Cu atoms is 7.0526(12)A. Adjacent dinuclear units are constituted through π-π interactions and C-H…O hydrogen-bonding interactions, fashioning the final 3-D supramolecular framework with 1-D open channels. Variable-temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic exchange interactions between CuⅡ ions.     

一维链状配位聚合物[Cu(CH3COO)(C5H5N)2]n的合成与晶体结构

The coordination polymer [Cu(CH3COO)(C5H5N)2]n was synthesized and its crystal structure has been determined by X-ray diffraction technique.The crystal belongs to monoclinic,space group C2/c with a=1.183 2(1) nm,b=1.512 1(2) nm,c=1.3911(1) nm,β=97.137(3)°,V=2.469 6(4) nm3,C12H13CuN2O2,Mr=280.78,Z=8,Dc=1.510 g·cm-3,μ=1.759 mm-1,F(000)=1 152,R1=0.048 2 and wR2=0.122 5 for 1 515 observed reflections [1>2σ(Ⅰ)].In the crystal the copper(Ⅲ) atom is tetra-coordinated primarily by two oxygen atoms of two symmetry-related carbexyl groups of acetate anions and two nitrogen atoms of two pyridine ligands in a parallelogram fashion.All of the pyridine rings linked to Cu(1) and Cu(2) are arranged centrosymmetrically on Cu(1).The neighboring copper complex molecules are linked together by the carboxylate oxygen atom of acetate anions to form an infinite one-dimensional linear chain structure.Moreover,π-π stacking interactions between intrachain pyridine molecules play the crucial role in constructing of the supramolecular structure.CCDC:709977.     

Crystal Structure and Magnetic Properties of the Oxamidato-bridged Cu3 Complex Containing Macrocyclic Ligands

One novel oxamido-bridged trinuclear complex [Cu(CuL)2(ClO4)2] has been syn-thesized and structurally determined.It crystallizes in the monoclinic system,space group P21/n with a = 10.636(4),b = 11.645(4),c = 16.038(6) ,β = 91.029(5)°,V = 1986.2(12) 3,C38H32Cl2Cu3N8O12,Mr = 1054.24,Dc = 1.763 Mg/m3,μ(MoKα) = 1.802 mm-1,F(000) = 1066,Z = 2,the final R = 0.0328 and wR = 0.0882 for 3152 observed reflections.The crystal structure is a trinuclear complex in which the CuII ions are bridged by macrocyclic oxamide groups.C-H···O hydrogen bonding interactions link the trinuclear fragment to form a 2D supramolecular architecture.Magnetic measurements indicate that the compound is moderately antiferromagnetically coupled.     

Fluoro-ketones. II Reactions of fluorocarbon grignards and copper compounds with perfluoroalkylacid fluorides

The reactions between C₆F₅MgBr (I), p-BrC₆F₄MgBr (X), C₆F₅Cu (XXI), p-HC₆F₄Cu (XXII) and p-BrC₆F₄Cu (XV) with primary and secondary perfluoroalkylether acid fluorides were studied. The Grignard compounds react very slowly with the secondary acid halides (R_fCF(CF₃C(O)F) whereby competing reactions cause undesirable by-products and reduction of ketone yields. Primary acid halides (R_fCF₂C(O)F) react much faster with C₆F₅MgBr to give the ketone in improved yields. The organocopper compound react with either primary or secondary acid halides to give the ketone in excellent yields with no by-product formation from competing secondary reactions. Solvent, type of organometallic reagent and primary versus secondary acid fluoride are variables that influence product yield and product distribution.     

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper（Ⅱ） Complex：[Cu_6（DPPZ）_4（btc）_4（H_2O）_8]·5H_2O

A new hexanuclear copper(Ⅱ) complex,[Cu 6 (DPPZ) 4 (btc) 4 (H 2 O) 8 ]·5H 2 O (1,DPPZ=dipyrido[3,2-a:2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid),has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489(4),b=14.234(5),c=14.484(5),α=82.848(4),β=79.399(4),γ=73.646(4)°,V=2421.2(13) 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F(000)=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I > 2σ(Ⅰ).In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.     

一维梯子型链状有机双膦酸铜Cu_3{(C_5NH_(11))C(OH)(PO_3)_2}_2(H_2O)_4·4H_2O的合成和表征(英文)

本文报道了一个新的有机双膦酸铜化合物Cu3{(C5NH11)C(OH)(PO3)2}2(H2O)4·4H2O(1)的合成及结构。该化合物呈梯子型双链结构,由Cu(1)O5四方锥体和Cu(2)O6八面体通过{PO3C}四面体以共顶点方式连接而成。相邻的双链以几乎相互垂直的方式堆积,通过氢键作用形成了具有孔道的三维超分子网络结构,晶格水分子填充其中。磁性研究表明在铜离子间存在反铁磁相互作用。     

Hydrothermal Synthesis,Crystal Structure and Magnetic Behavior of a Novel 3D Supramolecular Complex [Cu（HDPPZC）（SO4）（H2 O）]2

In the title coordination compound,[Cu(HDPPZC)(SO4)(H2O)]2 (1,HDPPZC=dipyrido[3,2-a:2,3-c]-phenazine-2-carboxylic acid),has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,elemental analysis and magnetic susceptibility measurement.It crystallizes in triclinic,space group P1 with a=0.69485(6),b=0.76878(4),c=1.76638(13)nm,α=99.437(6),β=94.690(6),γ=95.735(6)o,V=0.92151(12) nm 3,Z=1,Cu2C38 H24 N 8S2O14,Mr=1007.85,Dc= 1.816 g·cm-3,F(000)=510,GOOF=0.988,the final R=0.0580 and wR=0.0689.The structural analyses reveal that complex 1 shows discrete dinuclear clusters,which are further linked by hydrogen bonding and π·π stacking interactions to form a three-dimensional supramolecular compound.Magnetic measurement shows ferromagnetic and antiferromagnetic exchange interactions in the sample.     

Mononuclear and polynuclear copper(I) complexes with a new N,N',S-donor ligand and with structural analogies to the copper thionein core

The N,N',S-donor ligand 4-methoxy-3,5-dimethyl-2-((3-(2-(methylthio)phenyl)-1H-pyrazol-1-yl)methyl)pyridine (L) was prepared from 2-(chloromethyl)-4-methoxy-3,5-dimethylpyridine hydrochloride and 3-(2-(methylthio)phenyl)-1H-pyrazole. The Cu(I) complexes [Cu2(L)2CH3CN][Cu(L)CH3CN](BF4)3 (1), [Cu(L)PPh3]BF4 (2), and [Cu6(L)2(C6F5S)6] (3) were prepared and characterized by X-ray crystallography (PPh3=triphenylphosphine, C6F5S-=pentafluorothiophenolate). The unit cell of compound 1 consists of cocrystallized mononuclear and dinuclear entities in which all of the copper atoms exhibit distorted tetrahedral coordination. Compound 2 is monomeric with L bound in the kappa3-N,N',S mode and a PPh3 molecule that completes the coordination environment. Compound 2 presents a fluxional behavior in CDCl3 solution due to the boat inversion of the six-membered N,N' chelate ring (DeltaH=+43.6(3) kJ mol(-1), DeltaS=-16(1) J mol(-1) K(-1)). Crystallization of 3 in acetonitrile leads to a polynuclear structure that contains a CH3CN molecule coordinated to one of the copper atoms: [Cu6(L)2(C6F5S)6CH3CN] (3a). The core of 3a partially resembles a {Cu4S6} adamantane-like moiety, the only difference being that the Cu-NCCH3 interaction leads to the opening of the cluster by disrupting a Cu-Cu interaction. Part of this assembly is found in the yeast metallothionein copper(I)-cysteinate core whose crystal structure has recently been reported. Two additional [Cu(L)]+ peripheral moieties interact with the cluster by means of bridging thiolates. ESI-mass spectrometry, conductivity measurements, and 1H/19F pulsed gradient spin echo (PGSE) NMR experiments suggest that 3a dissociates in acetonitrile solution: 3a+CH3CN-->[Cu4(C6F5S)6]2-+2[Cu(L)CH3CN]+. The stability of the cluster with respect to the hypothetical mononuclear species, [Cu(L)(C6F5S)], is confirmed by DFT calculations (B3LYP), which illustrate the exergonic character of the reaction: 6[Cu(L')(C6H5S)]-->[Cu6(L')2(C6H5S)6]+4L' (DeltaG298=-58.6 kJ mol(-1), where L' and C6H5S- are simplified models for L and C6F5S-, respectively). The energetics pertinent to the ionic dissociation of the cluster in acetonitrile is computed using the polarizable continuum model (PCM) approach.     

Syntheses of highly fluorinated 1,3,5-triazapentadienyl ligands and their use in the isolation of copper(I)-carbonyl and copper(I)-ethylene complexes

Fully fluorinated triazapentadienyl ligand [N{(C3F7)C(C6F5)N}2]- and the related [N{(C3F7)C(2-F,6-(CF3)C6H3)N}2]- have been synthesized in good yield via a convenient route and used in the isolation of three- and four-coordinate copper(I)-carbon monoxide complexes. They show fairly high nu(CO) values (>2100 cm(-1)), indicating the presence of electron-poor Cu sites. The copper(I)-ethylene adduct [N{(C3F7)C(C6F5)N}2]Cu(C2H4), featuring a three-coordinate Cu site, has also been synthesized using [N{(C3F7)C(C6F5)N}2]CuNCCH3 and C2H4.     

Intra and intermolecular magnetic interactions in a series of dinuclear Cu(II)/hxta complexes [H5hxta = N,N'-(2-hydroxy-1,3-xylylene)-bis-(N-carboxymethylglycine)]: correlation of magnetic properties with geometry

Nine dinuclear copper(II) complexes with hxta5- ligands [H5hxta = N,N'-(2-hydroxy-1,3-xylylene)-bis-(N-carboxymethylglycine)]: [Cu2(MeO-hxtaH)(H2O)2] x 4H2O (1), [Na(micro-H2O)2(H2O)6][Cu2(Cl-hxta)(H2O)3]2 x 6H2O (2), [Cu(H2O)6][Cu2(Me-hxta)(H2O)2](NO3) x 2H2O (3), [Cu2(R-hxtaH)(H2O)3] x 3H2O [R = Cl (4), CH3 (5), and MeO (6)], [Cu2(MeO-hxtaH2)(micro-X)(CH3OH)] x 3CH3OH [X = Cl (7), Br (8)] and K5Na(micro-H2O)10[Cu2(micro-CO3)(Me-hxta)]2 x 4H2O (9), have been synthesized and structurally characterized. In complexes 4-7, the dinuclear units are linked via novel pairwise supramolecular interactions involving the ligand carboxylate groups. The intra- and intermolecular magnetic interactions have been quantified, and the coupling constants have been related to the structural geometries.     

Hydrothermal Synthesis, Crystal Structure and Magnetic Property of a Novel Pentanuclear Copper(II) Complex:[Cu_5(SIP)_2(HSIP)_2(H_2O)_(18)](H_2O)_5

The pentanuclear complex, Cu5(SIP)2(HSIP)2(H2O)18(H2O)5(H3SIP = 5-sulfoi-sophthalic acid), has been synthesized by the hydrothermal reaction of CuCl2 with NaH2SIP at 160 ℃, and characterized by single-crystal X-ray diffraction and IR spectrum.The crystal of the complex crystallizes in a triclinic system, space group P1-, with a = 7.0018(5), b = 11.9725(8), c = 19.0424(13) , α = 78.8540(10), β = 85.1710(10), γ = 83.6080(10)o, V = 1553.24(19) 3, Z = 1, C32H60O51S4Cu5, Mr = 1706.74, Dc = 1.825 g/cm3, μ = 1.937 mm-1, F(000) = 869, the final R = 0.0709 and wR = 0.1503 for 4235 observed reflections with I > 2σ(I).The five Cu2+ ions are connected by two symmetry-related tridentate SIP3-ligands and charge-balanced by two monodentate HSIP2-ligands, giving a discrete pentanuclear structure.The pentanuclear copper molecules are linked by hydrogen bonds to form a three-dimensional supramolecular structure.The temperature-dependent magnetic susceptibility data revealed weak ferromagnetic magnetic interactions between the Cu2+ ions.     

Hydrothermal Synthesis, Crystal Structure and Magnetic Property of a Novel Pentanuclear Copper(Ⅱ) Complex: [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5

The pentanuclear complex, [Cu5(SIP)2(HSIP)2(H2O)18](H2O)5 (H3SIP=5-sulfoi-sophthalic acid), has been synthesized by the hydrothermal reaction of CuCl2 with NaH2SIP at 160 ℃, and characterized by single-crystal X-ray diffraction and IR spectrum. The crystal of the complex crystallizes in a trielinic system, space group P1, with a = 7.0018(5), b = 11.9725(8), c = 19.0424(13) A, α = 78.8540(10), β = 85.1710(10),γ = 83.6080(10)~, V = 1553.24(19) A3, Z = 1, C32H60O51S4Cu5, Mr= 1706.74, Dc= 1.825 g/cm3,μ = 1.937 mm-1, F(000) = 869, the final R = 0.0709 and wR = 0.1503 for 4235 observed reflections with I > 2σ(I). The five Cu2+ ions are connected by two symmetry-related tridentate SIP3- ligands and charge-balanced by two monodentate HSIP2- ligands, giving a discrete pentanuclear structure. The pentanuclear copper molecules are linked by hydrogen bonds to form a three-dimensional supramolecular structure. The temperature-dependent magnetic susceptibility data revealed weak ferromagnetic magnetic interactions between the Cu2+ ions.     

Supramolecular assemblies of dimolybdenum transoids built by Mo2-enhanced perfluorophenyl-perfluorophenyl synthons

Two supramolecular assemblies were developed by the dimmolybdenum paddlewheel complex trans-Mo(2)(DAniF)(2)(O(2)CC(6)F(5))(2) (1) (ancillary ligand DAniF = N,N'-di-(p-anisyl)formamidinate) through intermolecular offset face to face C(6)F(5)···C(6)F(5) interactions. The two networks are different because of the presence and absence of tetrahydrofuran (THF) axial coordination to the Mo(2) units, but feature commonly short interplanar distances between the two paired perfluorophenyl groups, that is, 3.30 ? and 3.23 ?, respectively, which are similar to the shortest intermolecular C···F contacts between two atoms in meta and ortho positions. Consistently, as indicated by the Mulliken population analysis, the dipole moments for the meta and ortho C-F bonds are considerably enlarged because the pentafluorobenzoate groups are bonded to the dimetal unit. In comparison, X-ray structural and theoretical analyses were also made for the parent molecule pentafluorobenzoic acid. The resultant data show that charge distribution on the perfluorophenyl group has a major influence on the C(6)F(5)···C(6)F(5) binding mode. Therefore, it is evidenced that the dimetal unit plays a role in further polarizing the highly polarized C-F bonds and the intermolecular perfluorophenyl-perfluorophenyl interactions are dominated by the C···F dipole-dipole interaction, rather than aromatic-aromatic π-π stacking.     

Hydrothermal Synthesis and Crystal Structure of a Copper Complex

The title compound [Cu(IB)2]n·n(H2O) 1 was synthesized via the hydrothermal reaction of CuSO4·5H2O and NaOH with 4-(1H-Imidazol-1-yl)benzoic acid(HIB),and character-rized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in monoclinic,space group C2/c with a = 14.349(7),b = 5.977(3),c = 21.368(9) ,β = 104.956(9)o,V = 1770.5(2)3,Z = 4,C20H16CuN4O5,Mr = 455.92,Dc = 1.710 g/cm3,F(000) = 932 and μ(MoKα) = 1.279 mm-1.The final R = 0.0337 and wR = 0.0888 for 1972 observed reflections with Ⅰ 2σ(Ⅰ) and R = 0.0369 and wR = 0.0926 for all data.X-ray diffraction reveals that the IB ligand links the Cu(Ⅱ) atoms into a double stranded chain.The extensive supramolecular interactions lead to the formation of an infinite 2D structure.     

Aurophilicity versus mercurophilicity: impact of d10-d10 metallophilic interactions on the structure of metal-rich supramolecular assemblies

Treatment of U-shaped, binuclear Cu(I) complexes 1,1' (1, counterion: BF(4)(-); 1', counterion: PF(6)(-)) with metal cyanide linear linkers K[Au(CN)(2)] (3) and Hg(CN)(2) (4) lead to formation of new supramolecular assemblies 5,5' and 6,6', respectively, in good yield. These derivatives have been characterized by NMR spectroscopy, IR, and X-ray diffraction studies. Derivative 5,5' are supramolecular metallacycles in which intramolecular aurophilic interactions between the Au(I) metal centers of the linkers are observed. Derivative 5 crystallizes as a single solid phase, whereas derivative 5' is characterized in the solid state as four different pseudo-polymorphs (5'a-d). Notably in the case of phase 5'd, a dimer of supramolecular metallacycles bounded by intermolecular aurophilic interactions is formed. Conversely, derivatives 6,6' present large structural diversity depending on the nature of the counterion. Derivative 6 is a supramolecular rectangle in which the Hg(II)-Hg(II) metal distance suggests mercurophilic interaction, whereas 6' crystallizes as two different pseudo-polymorphs 6'a,b, that is, a one-dimensional coordination polymer and one oligomer with no short Hg(II)-Hg(II) metal contacts, respectively. In derivatives 6,6', short contacts between the Hg(II) metal centers and fluorine atoms of the counterions are also observed, which may explain the counterion structural dependence of these supramolecular assemblies based on Hg(II) metal cyanide linker. Comparison of the different solid-state structures characterized highlights the importance of weak secondary interactions between the linkers for the formation supramolecular metallacycles from molecular clips 1,1' and suggests the range of energies required for these interactions to form metallacycles and to induce self-aggregation.     

Synthesis and Crystal Structure of a Copper(Ⅱ) Compound Constructed by N-(4,6-Dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea

A copper(Ⅱ ) complex Cu(L)2(NO3)2 constructed by the L (L = N-(4,6-dime- thoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea) ligand crystallizes in monoclinic, space group C2/c with a = 16.2416(16), b = 9.1385(7), c = 22.0008(18) , β = 108.077(2)o, V = 3104.3(5)3, Dc = 1.627 g/cm3, Z = 4, C20H28CuN10O14S2, Mr = 760.18, μ(MoKα) = 0.920 mm–1, F(000) = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections (I > 2σ(I)). X-ray diffraction shows the existence of weak complementary intramolecular N–H…O (DA) hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu(II) ion, intermolecular C–H…O hydrogen bonds and weak π…π stacking interactions, leading to the formation of a multi-dimen- sional supramolecular network.     

Self-assembly of polyoxometalate-based metal organic frameworks based on octamolybdates and copper-organic units: from Cu(II), Cu(I,II) to Cu(I) via changing organic amine

Six polyoxometalate (POM)-based hybrid materials have been designed and synthesized based on octamolybdate building blocks and copper-organic units at different pH values under hydrothermal conditions, namely, [H2bbi][Cu(II)(bbi)2(beta-Mo8O26)] (1), [Cu(II)(bbi)2(H2O)(beta-Mo8O26)0.5] (2), [Cu(II)(bbi)2(alpha-Mo8O26)][Cu(I)(bbi)]2 (3), [Cu(II)Cu(I)(bbi)3(alpha-Mo8O26)][Cu(I)(bbi)] (4), [Cu(I)(bbi)]2[Cu(I)2(bbi)2(delta-Mo8O26)0.5][alpha-Mo8O26]0.5 (5), and [Cu(I)(bbi)][Cu(I)(bbi)(theta-Mo8O26)0.5] (6), where bbi is 1,1'-(1,4-butanediyl)bis(imidazole). Their crystal structures have been determined by X-ray diffraction. In compound 1, the bbi ligands with bis-monodentate coordination modes link Cu(II) cations to generate a 2D copper-organic unit with (4, 4) net, which is pillared by the (beta-Mo8O26)(4-) anions to form a 3D framework with alpha-Po topology. The similar copper-organic units are connected alternately by (beta-Mo8O26)(4-) anions to generate a 3D 2-fold interpenetrating (4,6)-connected framework with (4(4) x 6(2))(4(4) x 6(10) x 8) topology in compound 2. Compounds 3 and 4 are supramolecular isomers with polythreaded topology. If Cu (I)...O interactions are considered, the structure of 3 is a novel self-penetrating (3,4,6)-connected framework with (5(2) x 8)2(5(4) x 6 x 8)(4(4) x 6(10) x 10) topology, and the structure of 4 is a (4,6)-connected framework with (4(2) x 6(3) x 7)(5.6(4) x 8)(4(2) x 5(6) x 6(6) x 8)(4(2) x 5(6) x 6(4) x 7 x 8(2)) topology. Different from compounds 3 and 4, compounds 5 and 6 are supramolecular isomers with polythreaded topology based on different octamolybdate isomers. By careful inspection of the structures of 1-6, it is believed that various copper-organic units, which are formed by bbi ligands combined with Cu(II)/Cu(I) cations, octamolybdates with different types and coordination modes, and the nonbonding interactions between polyanions and copper-organic units are important for the formation of the different structures. In addition, with step by step increasing of the amount of organic amine, we have achieved the transformation of Cu(II) ions into Cu(I) ones in different degrees in POMs-based metal-organic frameworks (MOFs) for the first time. The infrared spectra, X-ray powder diffraction, and thermogravimetric analyses have been investigated in detail for all compounds, and the luminescent properties have been also been investigated for compounds 3 and 4.