Organic–inorganic hybrid materials constructed from Cu(II)–organonitrogen coordination complex cations and oxovanadium-arsonate subunits

Inorganica Chimica Acta 363 (2010) 3254–3260

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Organic–inorganic hybrid materials constructed from Cu(II)–organonitrogen coordination complex cations and oxovanadium-arsonate subunits Paul DeBurgomaster a, Hongxue Liu b, Charles J. O’Connor b, Jon Zubieta a,* a b

Department of Chemistry, Syracuse University, Syracuse, NY 13244, United States Advanced Materials Research Institute, College of Sciences, University of New Orleans, New Orleans, LA 70148, United States

a r t i c l e

i n f o

Article history: Received 19 April 2010 Accepted 7 June 2010 Available online 7 July 2010 Keywords: Organic–inorganic hybrid material Copper vanadium oxide Hydrothermal synthesis

a b s t r a c t The hydrothermal reactions of NH4VO3, Cu(NO3)2H2O or Cu(CH3CO2)2H2O As2O5 and the appropriate organonitrogen ligand in the presence of HF as mineralizer yield a series of bimetallic oxides of the Cu/ V/O/As family. The materials [Cu(bpy)(VO2)(AsO4)] (1) and [Cu(bpy)VO2(OH)(AsO4H)]H2O (2H2O) are one-dimensional (bpy = 2,20 -bipyridine). While phase 1 is constructed from fVO2 ðAsO4 Þgn 2n chains decorated by {Cu(bpy)}2+ groups, compound 2 consists of {V2O4(OH)2(AsO4H)2}2 clusters linked through {Cu(bpy)}2+ subunits. In contrast, the structure of [Cu2(bpyrm)(VO2)2(AsO4)2]H2O (3H2O) is three-dimensional, consisting of fVO2 ðAsO4 Þgn 2n layers, linked through {Cu2(bpyrm)}4+ rods (bpyrm = bipyrimidine). Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction Hybrid materials combine the unique characteristics of their organic and inorganic constituents to provide novel solid state structures that may possess composite or new properties [1–11]. The inorganic oxides are an extensive family of materials which demonstrates the structural consequences of the incorporation of organic substrates into the oxide architecture in materials such as zeolites [12,13], mesoporous MCM-41 materials [14,15] and transition metal oxides and phosphates [1,16,17]. One approach to the modification of inorganic oxide structures is to introduce the organic component as a ligand to a secondary metal site, which functions as an integral subunit of the covalent architecture of the solids. In such materials, the overall structure will reflect the coordination preferences of the secondary metal site, which may be manifested in the polyhedral type adopted, the ligand donor group ligation, the geometric constraints of the ligand, and the degree of aggregation into oligomeric substructures. This approach has been extensively explored in the chemistry of the oxomolybdenum and oxovanadium organophosphonates [18–56]. In contrast, the structural chemistry of oxovanadium phosphate materials incorporating secondary metal–ligand coordination complex substructures remains relatively unexplored. Small series of materials of the (M(II)–organonitrogen ligand)/VxOy /PO4 3 system (M(II) = Cu(II) and Zn(II) demonstrated considerable structural diversity, reflecting in part the denticity, steric bulk and coordination geometry of the ligand and the coordination preferences of * Corresponding author. E-mail address: [email protected] (J. Zubieta). 0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2010.06.005

the secondary metal [57–63]. On the other hand, the analogous materials with phosphate replaced by arsonate, (M(II)–organonitrogen ligand)/VxOy /AsO4 3 , are almost unknown [64]. As part of our continuing investigations of the hydrothermal and structural chemistry of transition metal oxides with EO4 3 and M(II)-ligand components, we have prepared three materials of the (Cu(II)– organonitrogen)/VxOy /AsO4 3 family: the one-dimensional [Cu(bpy)(VO2)(AsO4)] (1) and [Cu(bpy)VO2(OH)(AsO4H)]H2O (2H2O) and the three-dimensional [{Cu2(bpyrm)}(VO2)2(AsO4)2]H2O (3H2O), where bpy = 2,20 -bipyridine and bpyrm = bipyrimidine. 2. Experimental section 2.1. General considerations All chemicals were used as obtained without further purification: vanadium(V) oxide, arsenic(V) oxide, cupric acetate hydrate, cupric nitrate hydrate, 2,20 -dipyridine, 2,20 -bipyrimidine and hydrofluoric acid (48–51%) were purchased from Aldrich. All hydrothermal syntheses were carried out in 23 mL poly(tetrafluoroethylene) lined stainless steel containers under autogenous pressure. Water was distilled above 3.0 MX in-housing using a Barnstead Model 525 Biopure Distilled Water Center. The initial and final pH of the reactions were measured using Hydrion pH sticks. 2.2. Synthesis of [Cu(bpy)(VO2)(AsO4)] (1) A solution containing NH4VO3 (0.097 g, 0.83 mmol), cupric nitrate hydrate (0.091 g, 0.39 mmol), arsenic(V) oxide (0.051 g, 0.22 mmol), 2,20 dipyridyl (0.071 g, 0.46 mmol), H2O (10.00 mL,

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554.94 mmol) and HF (100 lL, 2.90 mmol) in the mole ratio 3.77:1.77:1.00:2.09:2522:13.18 was heated to 180 °C for 72 h. Initial and final pH values of 2.5 and 2.0 were recorded. Blue blocks of 1 suitable for X-ray diffraction were isolated in 65% yield. IR (KBr pellet, cm1): 3115(w), 3056(w), 1601(m), 1568(w), 1474(m), 1446(m), 1317(w), 1250(w), 1160(m), 1034(w), 962(s), 947(s), 919(s), 894(s), 861(m), 761(s), 717(m), 538(w), 513(w), 470(w). Anal. Calc. for C10H8AsCuN2O6V: C, 27.2; H, 1.83; N, 6.34. Found: C, 27.4; H, 1.64; N, 6.32%. 2.3. Synthesis of [Cu(bpy)VO2(OH)(AsO4H)]H2O (2H2O) A solution of NH4VO3 (0.100 g, 0.85 mmol), cupric nitrate hydrate (0.090 g, 0.39 mmol), arsenic(V) oxide (0.046 g, 0.20 mmol), 2,20 dipyridyl (0.069 g, 0.44 mmol), H2O (10.00 mL, 554.94 mmol) and HF (200 lL, 5.80 mmol) in the mole ratio 4.25:1.95:1.00:2.20:2775:29.00 was heated to 120 °C for 72 h (initial pH: 2.0, final pH: 1.5). Green blocks of 2 were isolated in 70% yield. IR (KBr pellet, cm1): 3316(b), 3108(w), 3057(w), 1603(m), 1561(w), 1473(w), 1448(m), 1317(w), 1251(w), 1174(w), 1036(w), 982(w), 893(m), 829(s), 794(m), 772(m), 728(w), 523(m). Anal. Calc. for C10H12AsCuN2O8V: C, 25.4; H, 2.53; N, 5.87. Found: C, 25.1, H; 2.43; N, 5.67%. 2.4. Synthesis of [Cu2(bpyrm)(VO2)2(AsO4)2]H2O (3H2O) The reaction of NH4VO3 (0.103 g, 0.88 mmol), cupric acetate hydrate (0.102 g, 0.56 mmol), arsenic(V) oxide (0.101 g, 0.44 mmol), 2,20 bipyrmidine (0.042 g, 0.27 mmol), H2O (10.00 mL, 554.94 mmol) and HF (100 lL, 2.90 mmol) in the mole ratio 3.26:2.07:1.63:1.00:2055:10.74 at 150 °C for 4 days afforded green plates of 3 in 40% yield (initial pH: 2.5, final pH: 2.0). IR (KBr pellet, cm1): 3486(b), 3097(m), 1590(m), 1560(w), 1414(m), 1226(w), 1040(w), 944(s), 913(s), 819(m), 762(s), 747(m), 685(m), 519(w). Anal. Calc. for C8H8As2Cu2N4O13V2: C, 12.9; H, 1.08; N, 7.50. Found: C, 13.1; H, 0.83; N, 7.55%. 2.5. X-ray crystallography Structural measurements were performed on a Bruker-AXS SMART-CCD diffractometer at low temperature (90 K) using graphite-monochromated Mo Ka radiation (kMo Ka = 0.71073 Å) [65]. The data were corrected for Lorentz and polarization effects and absorption using SADABS [66]. The structures were solved by direct methods. All non-hydrogen atoms were refined anisotropically. After all of the non-hydrogen atoms were located, the model was refined against F2, initially using isotropic and later anisotropic thermal displacement parameters. Hydrogen atoms were introduced in calculated positions and refined isotropically. Neutral atom scattering coefficients and anomalous dispersion corrections were taken from the International Tables, Vol. C. All calculations were performed using SHELXTL crystallographic software packages [67,68]. Crystallographic details have been summarized in Table 1. Atomic positional parameters, full tables of bond lengths and angles, and anisotropic temperature factors are available in Supplementary material. 3. Results and discussion 3.1. Syntheses and infrared spectroscopy The compounds of this study were prepared by conventional hydrothermal methods, which have been demonstrated to be particularly effective in the preparation and isolation of organic–inor-

Table 1 Summary of crystallographic data for the structures of [Cu(bpy)(VO2)(AsO4)] (1), [Cu(bpy)VO2(OH)(AsO4H)]H2O (2H2O) and [Cu2(bpyrm)(VO2)2(AsO4)2]H2O (3H2O).

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc (g cm3) l (mm1) T (K) Wavelength R1 wR2

1

2H2O

3H2O

C10H8AsCuN2O6V

C10H12AsCuN2O8V

C4H4AsCuN2O6.50V

441.58

477.62

373.49

triclinic  P1 5.6783(7) 10.2533(13) 11.7581(14) 72.638(2) 80.446(2) 86.637(2) 644.29(14) 2 2.276 4.952 90(2) 0.71073Å 0.0245 0.0609

triclinic  P1 7.0433(11) 10.4671(17) 10.9191(18) 103.311(3) 108.174(3) 99.807(3) 718.3(2) 2 2.208 4.461 90(2) 0.71073Å 0.0659 0.1706

monoclinic C2/c 19.3633(13) 7.7905(5) 11.6914(8) 90 98.3350(10) 90 1745.0(2) 8 2.843 7.289 90(2) 0.71073Å 0.0187 0.0488

P P P P jF o  F c j= jF o j; wR2 = f ½wðF 2o  F 2c Þ2 = ½wðF 2o Þ2 1=2 g R1 = (aP)2 + bP]; P = [Max(F 2o , O) + 2F 2c ]/3.

;

w = 1/[r2(F 2o ) +

ganic hybrid materials [69–74]. The reaction mixtures consisted of NH4VO3, As2O5, a copper(II) source, an appropriate organonitrogen chelate and HF. The HF is present as a mineralizer to promote solubility and crystal growth and does not appear as a component of the final products. It is quite common for the products of hydrothermal reactions to be sensitive to reaction conditions. Thus, compounds 1 and 2 were prepared from the same starting materials at similar stoichiometries, but the reaction mixture of 1 was heated at 180 °C, while that for 2 was kept at 120 °C. The infrared spectra of 1 and 3 exhibit two strong bands in the 910–945 cm1 region attributed to msym and masym for the cis(VO2) unit of the tetrahedral {VO4} subunit. In contrast, the {VO6} group of compound 2 exhibits only a medium intensity band at 893 cm1 associated with m(V@O). A series of bands in the 700–900 cm1 range for all three compounds may be attributed to m(As–O), m(V–O–V) and m(As–O–V). 3.2. Structural studies As shown in Fig. 1, the structure of 1 consists of two infinite fðVO2 ÞðAsO4 Þgn 2n chains with {(Cu(bpy)}2+ subunits serving to passivate the surface and to link the two chains. Each vanadium(V) tetrahedron shares a vertex with each of two adjacent {AsO4} tetrahedra and with a Cu(II) site. A terminal oxo-group projects away from the chain. Each {AsO4} tetrahedron links two vanadate sites of a chain and shares its remaining oxygen vertices with two copper sites. The square pyramidal geometry of the Cu(II) site is defined by the bipyridine nitrogen donor and the arsonate oxo-groups in the basal plane, with an apical oxo-group shared with a {VO4} unit. The copper sites bridge the two fðVO2 ÞðAsO4 Þgn 2n chains. The one-dimensional structure of 1 is analogous to that of the phosphate phase [Cu(bpy)(VO2)(PO4)] [58]. The structure of [Cu(bpy)VO2(OH)(AsO4H)]H2O (2H2O) is also one-dimensional. However, in this instance, the chain is constructed from {VO2(OH)(AsO4H)}2 clusters linked through {CuN2O3} square pyramids (Fig. 2). The cluster substructure contains a binuclear unit of edge-sharing {VO6} octahedra capped on either face by {AsO4H} tetrahedra. The vanadium coordination sphere consists of a terminal oxogroup, two trans-oxygen donors bridging to the {AsO4H} tetrahedra of the cluster, an oxo-group bridging to a copper site, and two

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Fig. 1. A mixed polyhedral and ball and stick representation of the structure of [Cu(bpy)(VO2)(AsO4)] (1). Colour scheme: orange tetrahedra, vanadium; blue polyhedra, copper; red tetrahedra, arsenic; red spheres, oxygen; light blue spheres, nitrogen; black spheres, carbon. The colour scheme is used throughout. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

trans-l3-hydroxo groups that bridge the vanadium sites and a copper center. As a result of this connectivity pattern, each binuclear vanadium unit links to four {Cu(bpy)}2+ sites. The {AsO4H}2 tetrahedra bridge the two vanadium octahedra of a binuclear unit and share a third vertex with a copper site. The fourth oxygen of the tetrahedron is protonated and pendant. The basal plane of the copper(II) square pyramid is defined by the bipyridyl nitrogen donors, an oxygen bridging to an arsenic site, and a l3-OH bridging the copper to the two vanadium sites of the binuclear unit. The apical position is occupied by a bridging oxo-group to a vanadium site of an adjacent vanadoarsonate cluster. The protonation site on the arsonate oxygen is revealed by the presence of significant electron density at a consistent position in the final Fourier map. Valence sum calculations [75] clearly identify the l3-oxygen site as a hydroxo group. In contrast to 1 and 2, the structure of 3H2O, shown in Fig. 3, is three-dimensional. The framework is constructed from fVO2 ðAsO4 Þgn n chains linked through {Cu2(bpyrm)}4+ rods. The chains are constructed from corner-sharing {VO4} and {AsO4} tetrahedra. Each {AsO4} subunit engages the remaining two vertices to corner-share to two {CuN2O3} square pyramids, while each {VO4} site also corner-shares to two additional copper sites. Consequently, adjacent fðVO2 ÞðAsO4 Þgn 2n chains are linked through copper sites into {Cu(VO2)(AsO4)}n layers, parallel to the bc crystal-

lographic plane. The structure may be described as copper vanadoarsonate layers linked through bipyrimidine ligands into a threedimensional architecture. In this sense, the structure may be viewed as a typical ‘‘buttressed” layer structure with alternating inorganic oxide layers and interlamellar organic domains. The copper sites exhibit {CuN2O4} ‘4 + 2’ six coordination, due to Jahn Teller elongation of the axial bonds. The equatorial plane is defined by two nitrogen donors of the bpyrm ligand and arsenic oxygen donors from adjacent chains. The axial positions are occupied by vanadium oxo-groups from adjacent chains. It can be instructive to compare the structures of the organic– inorganic hybrid materials of the (M(II)–organonitrogen ligand)/ VxOy/EO43 family to the parent MO(EO4) prototypes (M@V, Nb, Ta; E@P, As). X-ray diffraction studies have established that the latter constitute an isomorphous series of tetragonal forms, consisting of chains of weakly interacting {MO6} octahedra sharing corners with four {XO4} tetrahedra which link the {VO} sites to form {MOXO4}1 layers [76–80]. In the vanadate structures, the tetragonal layers are stacked to allow corner-sharing of the axial trans vertices of the {VO6} octahedra. The vanadium site is displaced from the centroid of the octahedron along the {O–V@O} axis to produce an alternation of long and short V–O bond distances of 2.85 Å and 1.58 Å, respectively. Alternatively, the structure may be described as {VO5} square pyramids and {XO4} tetrahedra in a layered structure, with weak V–O interactions between layers.

Fig. 2. A mixed polyhedral and ball and stick representation of the structure of [Cu(bpy)VO2(OH)(AsO4H)] (2).

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polyhedra, protonation of oxo-groups, and the flexibility of the V–O–E angles. Of course, the seeming absence of structural systematics is likely a reflection of the paucity of the data base for materials of this type. The vast hydrothermal parameter species and the possible variations in the M(II) and ligand components suggest that high throughput methods may be required to adequately explore the structural domains. 3.3. Magnetic susceptibility studies The temperature dependent magnetic data were collected at magnetic field of 1000 Oe in the 2–300 K temperature range after zero field cooling using a Quantum Design MPMS-XL-7 SQUID magnetometer. As shown in Fig. 4, the magnetic data for compound 1 show evidence for antiferromagnetic coupling and exhibit a local maximum at ca. 30 K. However, we were not able to obtain an acceptable fit using magnetic models consistent with the crystal structure. Antiferromagnetic coupling of Cu(II) sites in the binuclear {Cu2(AsO4)2} units of the chain of compound 1 is expected to be significant as it reflects the orientation of the copper basal planes for the ‘4 + 1’ axially distorted geometry. When the basal planes of the two copper atoms of the {Cu2(AsO4)2} unit are essentially coplanar, the overlap between dx2 y2 magnetic orbitals on each metal through the {–O–As–O–} bridges results in strong antiferromagnetic interactions. Compound 2 exhibits temperature dependent magnetic susceptibility consistent with the Heisenberg linear chain model with one S = 1/2 Cu(II) ion per formula weight. As shown in Fig. 5, the best fit conforms to Eq. (1), where y = |J|/kT and other parameters have the usual meaning [81]

v ¼ v0 þ vTI ¼ ð1  qÞ þq

Fig. 3. (a) A view of the structure of [{Cu2(bpyrm)}(VO2)2(AsO4)2] (3) in the ac plane; (b) a view normal to the {Cu(VO2)2(AsO4)2}1 plane (in the bc plane).

Ng 2 l2B SðS þ 1Þ þ vTI 3kT

ð1Þ

The calculated susceptibility has been corrected for exchange interaction zJ 0 between all spins as shown in Eq. (2).

v0 ¼ The introduction of secondary metal–ligand components serves to disrupt this layer motif, generally producing structures of lower dimensionality. As shown in Table 2, this structural influence of the secondary metal–ligand component is most dramatic when the ligand is a simple capping chelate, such as bipyridine or phenanthroline. Thus, the structures of [Cu(bpy)(VO2)(PO4)], [Cu(bpy)(VO2)(AsO4)] (1), [Cu(bpy)VO2(OH)(HAsO4)] (2), [Cu(phen)(VO2)(PO4)], [Zn(bpy)(VO2)PO4)] and {Zn(terpy)(VO2)(PO4)] are onedimensional. While two-dimensional structures are observed for [{Cu(phen)}2(VO2)3(OH)(PO4)2], [{Cu(phen)}2(VO)3(PO4)(HPO4)2] and [Zn(phen)(ZnVO)(PO4)2], the building blocks, such as the V–E–O subunit, are quite distinct from those of the [MO(EO4)] prototype. Three-dimensional structures are only observed when dipodal ligands, such as 4,40 -bipyridine and bipyrimidine, are used as in [Cu(4,40 -bpy)(VO2)(PO4)] and [Cu2(bpyrm)(VO2)2(AsO4)2]. While many of the structures share the simple formulation [M(ligand)(VO2)(EO4)], structural homologies are relatively uncommon. The diversity of structures reflects factors such as the coordination preference of the secondary metal, the demands of the ligand, the variable coordination polyhedra available to V(V), the potential for aggregation or polymerization of vanadium

Ng 2 l2B 0:25 þ 0:14995y þ 0:30094y2 kT 1:0 þ 1:9862y þ 0:68854y2 þ 6:0626y3

v0 1  ð2zJ 0 =Ng 2 l2B Þv0

ð2Þ

The calculated susceptibility was corrected for the exchange interaction zJ0 between all spins, using Eq. (3). The best fit gave g = 2.22, J/k = 6.13 K, zJ0 = 3.67 and vTI = 0.000124 emu/mol. The magnitude of J/k indicates weak coupling between Cu sites, an observation consistent with the structural requirement for spins to communicate through {Cu–O–V–O–Cu} bridges. The magnetic susceptibility of compound 3 conformed to the Heisenberg dimer model of Eq. (3), for one S = 1/2 Cu(II) ion per formula weight and corrected for the exchange interaction between spins using Eq. (2)

v ¼ v0 þ vTI ¼ ð1  qÞ

Ng 2 l2B 2e2x Ng 2 l2B SðS þ 1Þ þ vTI þq 2x 3kðT  hÞ kT 1 þ 3e

ð3Þ

The best fit (Fig. 6) gives g = 2.25, J/k = 115.71 K, q = 2.56%, zJ0 = 17.70 and vTI = 0.00000667 emu/mol. The effective magnetic moment at 300 K, leff = (8v0T)1/2 is 1.70 lB, corresponding to one Cu(II) site per formula. The J/k parameter clearly reveals strong antiferromagnetic coupling for 3. The magnitude of the antiferromagnetic coupling in materials with {Cu2(bpyrm)}4+ units reflects the orientation of

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Table 2 Comparison of structural characteristics of the [VO(EO4)] prototype and organic–inorganic hybrids of the type (M(II)–organonitrogen ligand)/VxOy/EO4 (E = P, As).

a

Compound

Dimensionality

Vanadium geometrya

V–E–O, E = As, P substructure

VO(PO4)

3D

a-[Cu(bpy)(VO2)(PO4)]

1D

{VO6} axially distorted octahedra, forming chains of weakly interacting polyhedra Isolated {VO4} tetrahedra

Layer of {VO5} square pyramids, each corner-sharing with four (PO4) tetrahedra fðVO2 ÞðPO4 Þgn 2n chain

b-[Cu(bpy)(VO2)(PO4)]

1D

Isolated {VO4} tetrahedra

[Cu(bpy)(VO2)(AsO4)] (1)

1D

Isolated {VO4} tetrahedra

{(VO2)2(PO4)2}4 clusters with {V2P2O4} rings fðVO2 ÞðAsO4 Þgn 2n chains

[Cu(dpa)(VO2)(PO4)]

1D

Isolated {VO4} tetrahedra

[Cu(phen)(VO2)(PO4)]

1D

Isolated {VO4} tetrahedra

[Cu(bpy)VO2(OH)(AsO4H)] (2) [{Cu(bpy)}4V4O11(PO4)2]

1D

Binuclear unit of edge-sharing {VO6} octahedra Octanuclear units of cornersharing {VO4} tetrahedra

1D

[71]

[58]

{Cu(bpy)} units link two adjacent chains into double chain motif Clusters linked by {Cu(dpa)}2+ groups

This work [60]

Clusters linked by {Cu(phen)} groups

[58,59]

Vanadoarsonate clusters linked by {Cu(bpy)}2+ groups Chains decorated by {Cu(bpy)}2+ groups

This work [61]

{Cu(phen)(VO2)(PO4)}n chains

[59]

fðVO2 Þ3 ðH2 OÞðPO4 Þ2 gn 3n chains

{Cu(phen)(VO2)(PO4)}n chains

[63]

fðVOÞ3 ðPO4 ÞðHPO4 Þ2 gn 4n layer fV5 O11 ðAsO4 Þ2 gn 4n layer

{Cu(phen)}2+ groups decorate either face of the vanadophosphate layer

[59]

{Cu(phen)}2+ groups incorporated into the layer

[64]

{Cu(VO2)(PO4)}n layers bridged by 4,40 bipyridine ligands to give a pillared layer structure {Cu(VO2)(AsO4)}n layers with vanadoarsonate chains linked by copper sites; layers buttressed by bpyrm ligands Clusters linked through {Zn(bpy)}2+ sites

[58]

Clusters linked through {Zn(terpy)}2+ groups fðZnVOÞðPO4 Þ2 gn 2n layers, decorated with {Zn(phen)}2+ groups

[57]

4

{(VO2)2(PO4)2} clusters with {V2P2O4} rings {(VO2)2(PO4)2} clusters with {V2P2O4} rings {V2O4(OH)2(AsO4H)2}4 clusters fV4 O11 ðPO4 Þ2 gn 8n chains with {V4O4(PO4)2} cages linked through {V4O11}2 units fðVO2 Þ3 ðOHÞðPO4 Þ2 gn 4n chain

2D

[{Cu(phen)}2(VO)3(PO4) (HPO4)2]

2D

[{Cu(phen)}2V5O11(AsO4)2]

2D

[Cu(4,40 -bpy)(VO2)(PO4)]

3D

Edge- and corner-sharing V(IV) and V(V) square pyramids Isolated {VO4} tetrahedra

[{Cu2(bpyrm)}(VO2)2 (AsO4)2] (3)

3D

Isolated {VO4} tetrahedra

fVO2 AsO4 gn 2n chains

2D

Ref.

{Cu(bpy)} units link two adjacent chains into double chain motif Clusters linked by {Cu(bpy)}2+ groups

[{Cu(phen)}2(VO2)3(OH) (PO4)2] [{Cu(phen)}2(VO2)3(H2O) (PO4)2]

Isolated {VO4} tetrahedra and {VO5} square pyramids Isolated {V(V)O4} tetrahedral and {V(IV)O5} square pyramids Isolated V(IV) square pyramids and octahedra

Other structural details

{(VO2)2(PO4)2}4 clusters

[Zn(bpy)(VO2)(PO4)]

1D

Isolated {VO4} tetrahedra

[Zn(terpy)(VO2)(PO4)]

1D

Isolated {VO4} tetrahedra

fVO2 ðPO4 Þ2 gn 4n clusters {(VO)2(PO4)2}4 clusters

[Zn(phen)(ZnVO)(PO4)2]

2D

Isolated V(IV) square pyramids

{(VO)2(PO4)4}8 clusters

[61,62]

This work [57]

[58]

V in +5 oxidation state unless otherwise noted.

the copper basal plane for the ‘‘4 + 1” axially distorted square pyramid relative to the bipyrimidine plane. When the basal planes of the two copper atoms contain the cis-Cu–N bonds to the bipyrimidine and are essentially coplanar with the bipyrimidine plane, the

Fig. 4. Temperature dependence of the magnetic susceptibility v (circles) for compound 1 in the 2–300 K temperature range.

overlap between dx2 y2 magnetic orbitals on each metal through the bridging bipyrimidine ligand results in strong antiferromagnetic coupling [18,82,83].

Fig. 5. Temperature dependence of the magnetic susceptibility v (circles) and the effective magnetic moment leff (squares) for compound 2 in the 2–300 K temperature range. The inset shows the behavior of the inverse susceptibility 1/ v0 with temperature. The lines through the data are the fits to the Heisenberg linear chain model.

P. DeBurgomaster et al. / Inorganica Chimica Acta 363 (2010) 3254–3260 [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28]

Fig. 6. Temperature dependence of the magnetic susceptibility v (circles) and the effective magnetic moment leff (squares) for compound 3 in the 2–300 K temperature range. The lines through the data are the best fits to the Heisenberg dimer model.

[29] [30] [31] [32]

4. Conclusions

[33]

Hydrothermal methods have been used to prepare a small series of Cu(II)-ligand/VxOy /Hx AsO4 ð3xÞ materials. The structural diversity manifested by even this limited series reflects factors such as variable coordination polyhedra of vanadium, potential aggregation of vanadium polyhedra and the identity of the organonitrogen ligand to the Cu(II) component. This latter feature is most evident in the spatial expansion of compound 3 into threedimensions as a consequence of introducing a binucleating ligand. The series also demonstrates the variability of vanadoarsonate substructures, in this case one-dimensional fðVO2 ÞðAsO4 Þgn 2n chains, {V2O4(OH)2(AsO4H)2}2 clusters and fVO2 ðAsO4 Þgn 2n layers.

[34] [35] [36] [37] [38] [39] [40] [41] [42] [43] [44] [45]

Acknowledgment This work was supported by a grant from the National Science Foundation (CHE-0907787). The magnetic studies were supported by a grant from the Louisiana Board of Regents through contract number LEQSF(2007-12)-ENH-PKSFI-PRS-04.

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