(C5H6N)4[Be6(HPO3)8]·H2O: A low-density open-framework beryllium phosphite with multidirectional 12-ring channels

Employing the common pyridine (=py) solvent as the source of structure-directing agents (SDAs), a novel three-dimensional open-framework beryllium phosphite (Hpy)₄[Be₆(HPO₃)₈]·H₂O (1), has been solvothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. It crystallizes in the orthorhombic system, space group Pbca (No. 61), a = 20.0034(4) Å, b = 20.2188(4) Å, c = 20.9731(3) Å, V = 8482.5(3) Å³, and Z = 8. The alternating connection of BeO₄ tetrahedra and HPO₃ pseudopyramids give rise to a (3, 4)-connected network with multidirectional intersecting 12-ring channels. The compound possesses a low density and a new {4.8.10}{4².6.8.10.12}{4².6}₃{4².8.10².12}{4³.6².8} topology.     

Two zincophosphite frameworks templated by 1,4-diaminobenzene: syntheses and structures of C6N2H10·Zn(HPO3)2 and (C6N2H8)0.5·ZnHPO3

The solution-mediated syntheses and single crystal structures of C₆N₂H₁₀·Zn(HPO₃)₂ (I) and (C₆N₂H₈)_0.5·ZnHPO₃ (II) are reported. Slight variation of the synthesis conditions led to two quite different phases. I contains infinite chains of ZnO₄ and HPO₃ groups with the protonated organic moiety acting as a template and interacting with the chains by NH⋯O hydrogen bonds and possible CH⋯O interactions. In II, the neutral 1,4-diamino benzene molecule bonds to Zn (as a ligand) and an unusual composite, “pillared”, structure results, with the organic species bridging 6³ polyhedral sheets, although NH⋯O bonds are also present. Similarities and differences to other zinc phosphites and phosphates are briefly discussed for I and II. Crystal data: C₆N₂H₁₀·Zn(HPO₃)₂, M_r=335.48, monoclinic, C2/c (No. 15), a=17.2471 (14) Å, b=9.0720 (8) Å, c=7.6529 (6) Å, β=103.752 (2)°, V=1163.09 (7) Å³, Z=4, R(F)=0.038, wR(F²)=0.084. (C₆N₂H₈)_0.5·ZnHPO₃, M_r=199.42, orthorhombic, Pbca (No. 61), a=8.0314 (16) Å, b=8.1299 (16) Å, c=18.830 (4) Å, V=1229.5 (4) Å³, Z=8, R(F)=0.026, wR(F²)=0.055.     

Hydrothermal synthesis and characterization of a new organically templated three-dimensional open-framework gallium phosphate–phosphite (C6N2H18)2(C6N2H17)Ga15(OH)8(PO4)2(HPO4)12(HPO3)6·2H2O

Using H₃PO₃ as a phosphorus source and oxalic acid as a reducing agent, the first three-dimensional open-framework gallium phosphate–phosphite formula as (C₆N₂H₁₈)₂(C₆N₂H₁₇)Ga₁₅(OH)₈(PO₄)₂(HPO₄)₁₂(HPO₃)₆·2H₂O (1), has been hydrothermally synthesized in the presence of N,N,N′,N′-tetramethylenediamine (TMEDA) as a structure-directing agent. Compound 1 crystallizes in trigonal system with space group P ? 3, a = b = 19.046(3) Å, c = 8.3306(17) Å, γ = 120°, V = 2617.1(7) Å³, and Z = 1. Its 3-D network is based on alternated Ga-centered (GaO₄ tetrahedra, GaO₅ trigonal bipyramids, and GaO₆ octahedra) and P-centered (PO₄^3?, HPO₄^2?, and HPO₃^2?) units. Protonated organic amines and water molecules are located in the 12-membered ring channels.     

Synthesis of open-framework iron phosphates, [C5N2H14]2[FeIII2F2(HPO4)4]·2H2O and [C5N2H14][FeIII4(H2O)4F2(PO4)4], with one- and three-dimensional structures

The hydrothermal syntheses and structures of two new open-framework iron phosphates, [C₅N₂H₁₄]₂[Fe^III₂F₂(HPO₄)₄]·2H₂O, I, and [C₅N₂H₁₄][Fe^III₄(H₂O)₄F₂(PO₄)₄], II, are presented. While the structure of I consist of FeO₄F₂ octahedra and HPO₄ terahedra linked to form one-dimensional structure, that of II consist of FeO₄(H₂O)₂, FeO₄(H₂O)F, FeO₄F₂ and PO₄ units connected to give rise to a three-dimensional structure. The structure of I resembles the naturally occurring mineral tancoite while II resembles the iron phosphate, ULM-12, [C₆N₂H₁₄][Fe₄(PO₄)₂F₂(H₂O)₃]. Magnetic susceptibility studies indicate anti-ferromagnetic behavior in both the compounds with T_N=200 and 175 K for I and II, respectively. Crystal data: I, monoclinic, space group=P2₁/n (no. 14). a=7.2261(6), b=16.5731(14), c=11.0847(10) Å, β=97.265(2)°, V=1316.8(2) Å³, Z=4, ρ_calc=1.952 g cm⁻¹, μ_(MoKα)=1.446 mm⁻¹, R₁=0.0448 and wR₂=0.1141 for 1882 data [I>2σ(I)]; for II, monoclinic, space group=P2₁/n (no. 14). a=9.9691(3), b=12.4013(3), c=17.3410(3) Å, β=103.762(1)°, V=2082.32(9) Å³, Z=4, ρ_calc=2.576 g cm⁻¹, μ_(MoKα)=3.162 mm⁻¹, R₁=0.0510 and wR₂=0.1064 for 2979 data [I>2σ(I)].     

Two coordination polymers of manganese(II) isophthalate and their preparation,structures, and magnetic properties

Two manganese coordination polymers, [Mn₂(ip)₂(dmf)]·dmf (1) and [Mn₄(ip)₄(dmf)₆]·2dmf (2) (ip=isophthalate; dmf=N,N-dimethylformamide), have been synthesized and characterized. X-ray crystal structural data reveal that compound 1 crystallizes in triclinic space group P?1, a=9.716(3) Å, b=12.193(3) Å, c=12.576(3) Å, α=62.19(2)°, β=66.423(17)°, γ=72.72(2)°, Z=2, while compound 2 crystallizes in monoclinic space group Cc, a=19.80(3) Å, b=20.20(2) Å, c=18.01(3) Å, β=108.40(4)°, Z=4. Variable-temperature magnetic susceptibilities of compounds 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions.     

Two fumarato-bridged Co(II) coordination polymers: syntheses,crystal structures and properties of Co(H2O)4L and [Co3(H2O)4(OH)2L2]·2H2O with H2LHOOCCHCHCOOH

Two fumarato-bridged Co(II) coordination polymers Co(H₂O)₄L 1 and [Co₃(H₂O)₄(OH)₂L₂]·2H₂O 2 with H₂LHOOCCH CHCOOH were prepared. Complex 1 consists of polymeric chains _∞¹[Co(H₂O)₄(C₄H₂O₄)_2/2], which result from octahedrally coordinated Co atoms bridged by bis-monodentate fumarate anions and are assembled by interchain hydrogen bonds. Within 2, the edge-shared Co₂O₁₀ bi-octahedra are connected to the CoO₆ octahedra to form 1D cobalt oxide chains and 3D open framework generated from the chains inter-linked by bis-bidentate fumarate anions displays rhombic tunnels, which are filled with the lattice H₂O molecules. Thermal and magnetic behaviors of both the title coordination polymers are discussed. Crystal data: (1) monoclinic, P2₁/c, Z=4, a=7.493(1) Å, b=14.377(1) Å, c=7.708(1) Å, β=99.54(1)°, V=818.9(2) Å³, R₁=0.0304, and wR₂=0.0669 for 1487 observed reflections (I⩾2σ(I)) out of 1877 unique reflections; (2) monoclinic, P2₁/c, Z=2, a=6.618(1) Å, b=8.172(2) Å, c=15.578(3) Å, β=96.30(3)°, V=837.4(3) Å³, R₁=0.0360 and wR₂=0.0663 for 1442 observed reflections (I⩾2σ(I)) out of 1927 unique reflections.     

New compounds in the cesium sulfobromide rhenium octahedral cluster chemistry: syntheses and crystal structures of Cs4Re6S8Br6 and Cs2Re6S8Br4

The exploration of the CsReSBr system, in order to identify new phases based on octahedral cluster anions, has produced single crystals of Cs₄Re₆S₈Br₆ (1) (trigonal, space group P-6c2, a=9.7825 (3) Å, c=18.7843 (5) Å, V=1556.77 (1) ų, Z=2, density=5.09 g cm⁻³, μ=36.07 mm⁻¹) and Cs₂Re₆S₈Br₄ (2) (monoclinic, space group P2₁/n, a=6.3664 (1) Å, b=18.4483 (4) Å, c=9.3094 (2) Å, β=104.2618 (8)°, V=1059.69 (4) ų, Z=2, density=6.14 g cm⁻³, μ=45.83 mm⁻¹). These two compounds have been obtained by high-temperature solid state route. Their structures have been solved and refined from single crystal X-ray diffraction data. The structure of Cs₄Re₆S₈Br₆ presents isolated anionic cluster units inscribed in a (Cs⁺)₁₂ cuboctahedron and the one of Cs₂Re₆S₈Br₄ exhibits ReS^i-a,a-iRe inter-unit bridges. The framework of the latter presents then a strongly 1-D character.     

Ligand-based luminescence in lead-containing complexes: The effect of conjugated organic ligands on fluorescence

The asymmetrically substituted heterocyclic alkyne 5-(pyridin-3-ylethynyl) picolinate (P3PA) was synthesized via a one-pot Sonogashira coupling. After purification, P3PA was reacted with Pb(NO₃)₂ into the two-dimensional coordination polymer Pb(P3PA)₂(H₂O)₂ (1) under hydrothermal conditions. Coordination polymer 1 crystallizes into the monoclinic space group I2/a, with a = 15.5775(10) Å, b = 5.9949(4) Å, c = 24.8380(16) Å, and β = 90.7500(10)°. In addition, the luminescent fluorene-based ligands, fluorene-9-carboxylate (FCA) and fluorenone-2,7-dicarboxylate (FDCA), were incorporated into hybrid materials via coordination to the lead (II) cation. Coordination polymer Pb(FCA)₂ (2) crystallizes in the monoclinic space group P2₁/c (a = 8.0518(9) Å, b = 25.338(3) Å, c = 10.5842(12) Å, β = 94.913(2)°), and forms a 1-D polymeric chain. Coordination polymer Pb₃(FDCA)₃(H₂O)₃ (3) crystallizes in the triclinic space group P1 (a = 6.6990(5) Å, b = 10.1529(7) Å, c = 13.6935(9) Å, α = 81.884(2)°, β = 87.260(2)°, γ = 84.399(2)°), and forms pillared 3-D layers. These three compounds have been identified via single crystal X-ray diffraction and characterized via powder X-ray diffraction, UV–Vis spectroscopy, and fluorescence spectroscopy.     

Synthesis,crystal structure,and magnetic properties of K4Mn3(HPO4)4(H2PO4)2

A new layered compound, K₄Mn₃(HPO₄)₄(H₂PO₄)₂ (1), has been synthesized under hydrothermal conditions. It crystallizes in the monoclinic space group P2₁/n with a = 8.874(2) Å, b = 6.554(1) Å, c = 18.075(4) Å, and β = 93.39(3)°. The structure consists of zigzag [Mn₃O₁₄]_n chains of edge-sharing MnO₆ octahedrons and MnO₇ pentagonal bi-pyramids, which form layers of formula [Mn₃(HPO₄)₄(H₂PO₄)₂]^4? in the ab plane via H₂PO₄ and HPO₄ units with vertex-sharing. Potassium ions lie between these layers. Magnetic measurements indicate Curie–Weiss behavior above 6 K for 1. A Heisenberg model, with alternating exchange interactions J₁J₁J₂… within the chain and exchange interactions J₃J₃… between the chains, is proposed to describe the magnetic behavior.     

Intercalation of KCl into layered neptunyl and plutonyl iodates

The hydrothermal reaction of Np(IV) or Pu(IV) with KIO₄ and CsCl at 180°C for 1 day results in the formation of NpO₂(IO₃)₂·0.5KCl·3.25H₂O (1) or PuO₂(IO₃)₂·0.5KCl·2.5H₂O (2). The neutral layers in compounds 1 and 2 are isostructural with NpO₂(IO₃)₂·H₂O and PuO₂(IO₃)₂·H₂O, respectively. The Np and Pu centers are found in distorted pentagonal bipyramidal [AnO₇] environments that are formed from the ligation of NpO₂²⁺ or PuO₂²⁺ cations by iodate anions. There are two crystallographically unique pyramidal iodate anions in 1 and 2. One of these anions utilizes all three oxygen atoms to simultaneously bridge three neptunyl or plutonyl units. The second anion only bridges two actinyl units and has a terminal oxo atom. The bridging of the actinyl cations by iodate anions creates neutral _∞²[AnO₂(IO₃)₃] (An=Np, Pu) sheets that are separated by K⁺ cations, Cl⁻ anions, and water molecules. Crystallographic data (203 K, MoKα, λ=0.71073): 1, monoclinic, space group C2/c,a=21.537(5) Å, b=11.670(3) Å, c=7.315(2) Å, β=93.033(4)°, Z=4, R(F)=5.43% for 136 parameters with 1309 reflections with I>2σ(I); 2, monoclinic, space group C2/c, a=21.570(4) Å, b=11.656(2) Å, c=7.348(2) Å, β=94.00(3), Z=4, R(F)=4.92% for 148 parameters with 1317 reflections with I>2σ(I).     

Flux synthesis of (3,4)-connected zinc phosphites with different framework topologies

Two three-dimensional open-framework zinc phosphites, H₂aem·Zn₃(HPO₃)₄·0.5H₂O (1) and H₂apm·Zn₃(HPO₃)₄ (2), have been synthesized by a phosphorous acid flux method, where aem=4-(2-aminoethyl)morpholine and apm=4-(3-aminopropyl)morpholine. Compound 1 crystallizes in the monoclinic system, P2₁/c, a=9.5852(7) Å, b=20.3941(8) Å, c=10.5339(8) Å, β=94.125(9)°, V=2053.8(2) Å³, Z=4, R₁=0.0319, wR₂=0.0628. Compound 2 crystallizes in the monoclinic system, P2₁/n, a=8.589(2) Å, b=14.020(3) Å, c=16.606(3) Å, β=97.190(8)°, V=1983.9(7) Å³, Z=4, R₁=0.0692, wR₂=0.1479. Both compounds are based on (3,4)-connected networks with 8- and 12-ring channels, which are constructed from Zn₃(HPO₃)₄ clusters as the same secondary building units. These inorganic clusters are spatially organized by different structure-directing agents into different three-dimensional frameworks.     

Synthesis and structural characterization of a novel two-dimensional 3d-4f heterometallic coordination framework based on pentanuclear lanthanide cluster

A novel 3d-4f heterometallic coordination polymer, {[Tm₅(μ₃-OH)₂(BDC)₆(IN)₂Cu(H₂O)₂]·(H₂O)₃}_n (1) [BDC = benzene-1,2-dicarboxylate, IN = isonicotinate], has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. The compound crystallizes in monoclinic system, space group P2₁/c (No. 14), a = 13.7302(5) Å, b = 23.5428(3) Å, c = 21.5789(2) Å, β = 91.491(3)°, V = 6973.0(3) ų, and Z = 4. The structure exhibits unusual two-dimensional Tm-carboxylate layer, which is constructed from the expansion of novel pentanuclear {Tm₅} clusters. More interestingly, the heterometallic Cu(I) ions were successfully planted into such Ln-carboxylate layer by the bifunctional IN bridging ligands, resulting in the formation of an unprecedented 2D heterometallic lanthanide-transition-metal framework.     

A series of open-framework tin(II) phosphates: A[Sn4(PO4)3] (A=Na,K, NH4)

A new series of isostructural open-framework tin(II) phosphates with general formula A[Sn₄(PO₄)₃], where A=Na, K, NH₄, has been synthesized by hydrothermal methods. The crystal structures of NaSn₄(PO₄)₃ (I) and KSn₄(PO₄)₃ (II) have been solved by single crystal X-ray diffraction methods. Both phases crystallize in the trigonal space group R3c (#161) with Z=6 and cell parameters a=9.5508(13) Å, c=24.083(3) Å for I, and a=9.7124(11) Å, c=24.363(3) Å for II. The structure consists of a negatively charged [Sn₄(PO₄)₃]⁻ framework with channels running parallel to the a- and b-axes where the charge compensating A⁺ cations are located. An interesting feature is that half of the channels are empty due to the specific geometry of the SnO₃ units—the lone electron pair of the tin atoms “protrudes” in these channels thus preventing the insertion of A⁺. The new phases have also been characterized by infrared and thermogravimetric analyses.     

New three-dimensional (3,4)-net zincophosphites templated by linear diammonium cations: H3N(CH2)5NH3·Zn3(HPO3)4 and β-H3N(CH2)6NH3·Zn3(HPO3)4

The mild-condition syntheses, single-crystal structures and properties of H₃N(CH₂)₅NH₃·Zn₃(HPO₃)₄ and β-H₃N(CH₂)₆NH₃·Zn₃(HPO₃)₄ are reported. Both are constructed from (3,4)-nets of ZnO₄ tetrahedra and HPO₃ pyramids, sharing vertices to result in three-dimensional anionic open-frameworks. In both materials, the organic species interacts with the framework by way of N–H⋯O bonds. Crystal data: H₃N(CH₂)₅NH₃·Zn₃(HPO₃)₄, M_r = 620.22, orthorhombic, Pccn (No. 56), a = 9.5364 (9) Å, b = 21.8015 (19) Å, c = 9.1118 (7) Å, V = 1894.4 (3) Å³, Z = 4, R(F) = 0.044, wR(F²) = 0.111. β-H₃N(CH₂)₆NH₃·Zn₃(HPO₃)₄, M_r = 634.25, monoclinic, P2₁/n (No. 14), a = 8.7627 (1) Å, b = 13.8117 (2) Å, c = 16.6187 (3) Å, β = 92.680 (1)°, V = 2009.12 (5) Å³, Z = 4, R(F) = 0.072, wR(F²) = 0.187.     

One-dimensional coordination polymers generated from an oxadiazole-containing N,N′-bipyridine-type ligand and inorganic salts

Three new one-dimensional coordination polymers have been prepared using Hg(II), Ag(I) and Zn(II) inorganic salts in combination with 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L6). The compounds were characterized by single crystal X-ray diffraction, IR spectroscopy, and elemental analysis. In the solid state, compounds 1 and 3 (1: monoclinic, P2₁/n, a=5.5373(3) Å, b=16.7839(9) Å, c=16.8120(9) Å, β=92.8610(10)°, V=1560.52(15) ų, Z=4; 3: monoclinic, P2₁/n, a=7.2958(4) Å, b=11.7214(6) Å, c=16.3979(9) Å, β=101.1150(10)°, V=1375.99(13) Å³, Z=4) feature novel one-dimensional helical chain motif. Compound 2, however, (2: monoclinic, P2₁/c, a=5.5506(4) Å, b=16.5895(12) Å, c=16.6871(11) Å, β=95.424(2)°, V=1529.70(19) ų, Z=4) exhibits one-dimensional zigzag chain motif, which result from the different conformations adopted by the L6 ligand and also the different metal coordination geometry. The luminescent properties of three new compounds were investigated in the solid state.     

Syntheses and structures of two new M6Li8(N3)a6 cluster-unit based compounds: Cs4Re6S8(N3)6·H2O and Na2Mo6Br8(N3)6·2H2O

The two new cluster compounds, Cs₄Re₆S₈(N₃)₆·H₂O (1) and Na₂Mo₆Br₈(N₃)₆·2H₂O (2), have been prepared via solution chemistry route, starting from the Cs₄Re₆S₈Br₆CsBr and Mo₆Br₁₂ precursors synthesized by solid state chemistry techniques, and structurally characterized (crystal data: Cs₄Re₆S₈(N₃)₆·H₂O (1): Orthorhombic, space group Pnam, a=10.0651(1) Å, b=15.8856(2) Å, c=20.1714(3) Å, V=3225.2(7) Å³, Z=4, d_calc=4.48 g cm⁻³, μ=27.43 mm⁻¹; Na₂Mo₆Br₈(N₃)₆·2H₂O (2): Orthorhombic, space group Ibam, a=11.5643(3) Å, b=14.3959(5) Å, c=17.0340(7) Å, V=2835.8(2) ų, Z=4, d_calc=3.63 g cm⁻³, μ=13.91 mm⁻¹). Their structures revealed that in both cases, the M₆Lⁱ₈ cluster core remains unchanged in the starting and final compounds whereas the bromine apical ligands (Br^a) are substituted by N₃ azide groups leading to M₆Lⁱ₈(N₃)^a₆ cluster unit. The new Cs₄Re₆S₈(N₃)₆·H₂O is the first example of a compound containing an octahedral rhenium cluster coordinated to azide groups.     

Syntheses,structures and single-molecule magnetic behaviors of two dicubane Mn4 complexes

The reaction of MnX₂ · 4H₂O (X = Cl or Br) with 2,6-bis(hydroxymethyl)-4-methylphenol (H₃L) and NaOH in methanol solution yielded two tetranuclear manganese complexes, [Mn₄(HL)₄(MeOH)₄Cl₂] (1) and [Mn₄(HL)₄(MeOH)₄Br₂] (2). Both compounds crystallize in the monoclinic space group C₂/c with cell parameters: a = 26.0945(19) Å, b = 11.4999(8) Å, c = 21.2188(16) Å, β = 121.050(1)° and z = 4 for 1 · 2Et₂O; a = 25.8145(3) Å, b = 11.6734(2) Å, c = 21.3956(3) Å, β = 120.1277(6)° and z = 4 for 2 · 2Et₂O. Both complexes consist of a mixed-valence dicubane structure, which comprises two Mn^II and two Mn^III ions. Magnetic susceptibilities and magnetization of complexes 1 and 2 in the solid state indicate that two clusters have an S = 9 ground state. Frequency-dependent out-of-phase signals of alternating current magnetic susceptibilities were observed in the low temperature range (<3 K) for both complexes indicating a slow magnetic relaxation.     

Synthesis,structure and fluorescence of a novel three-dimensional inorganic–organic hybrid polymer constructed from trimetallic clusters and mixed carboxylate ligands

A new inorganic–organic hybrid framework coordination polymer, Cd₃(BDC)_0.5(BTC)₂(DMF)(H₂O)·3DMF·H₃O·H₂O 1, in which two carboxylate ligands, 1,4-benzenedicarboxylic acid (H₂BDC) and 1,3,5-benzenetricarboxylic acid (H₃BTC), coordinate with cadmium ions, has been synthesized under mild conditions and its structure solved by single-crystal X-ray diffraction (XRD) analysis. Polymer 1 crystallizes in the monoclinic system, space group P2₁/c (No. 14) with a=15.750(3) Å, b=14.501(3) Å, c=19.363(4) Å, β=113.67(3)°, V=4050.4(14) Å³, Z=4, R1=0.0374 and wR2=0.1148. Its structure revealed that the nine vertices of the secondary building units are linked by benzene rings from both H₃BTC and H₂BDC ligands to form a 3D network with 10×10 Å channels along [001] direction. Complex 1 is characterized by inductively coupled plasma analysis, powder XRD, infrared spectroscopy and thermogravimetric analysis. Polymer 1 exhibits intense fluorescence at 358 and 377 nm with λ_excitation=208 nm in the solid state at room temperature.     

Copper and cadmium phosphonates based on 2-quinolinephosphonate

Hydrothermal reactions of 2-quinolinephosphonic acid (1) and CuSO₄ or CdSO₄ result in two new compounds with formula Cu(2-C₉H₆NPO₃) (2) and Cd(2-C₉H₆NPO₃)(H₂O) (3). Compound 2 has a layer structure in which dimers of edge-sharing {CuO₄N} square-pyramids are linked by {CPO₃} tetrahedra through corner sharing. Compound 3 shows a new type of layer structure where chains of corner sharing {CdO₅N} octahedra are connected by {CPO₃} tetrahedra into an inorganic layer. The quinoline groups fill in the inter-layer spaces in both cases. Crystal data for 1: monoclinic, space group P2₁/c, a = 10.270(2) Å, b = 13.566(3) Å, c = 6.9818(16) Å, β = 101.916(4)°, V = 951.8(4) Å³, Z = 4. For 2: monoclinic, space group P2₁/c, a = 13.976(3) Å, b = 7.9398(18) Å, c = 7.8687(18) Å, β = 101.150(5)°, V = 856.7(3) Å³, Z = 4. For 3: monoclinic, space group P2₁/c, a = 17.164(4) Å, b = 5.4870(12) Å, c = 10.850(2) Å, β = 101.557(4)°, V = 1001.1(4) Å³, Z = 4. The magnetic measurement on 2 reveals a dominant antiferromagnetic exchange coupling between the Cu(II) centers. A quasi-reversible electrochemical reaction is observed for complex 2 immobilized on the surface of GC electrode, corresponding to the redox couple Cu²⁺/Cu⁺. The fluorescent properties of 1–3 are also investigated.