Small, beautiful and magnetically exotic: {V4W2}- and {V4W4}-type polyoxometalates Dalton Transactions COMMUNICATION Cite this: Dalton Trans., 2016, 45, 10519 Received 8th June 2016, Accepted 10th June 2016 DOI: 10.1039/c6dt02282k www.rsc.org/dalton Small, beautiful and magnetically exotic: {V4W2}- and {V4W4}-type polyoxometalates† Maren Rasmussen,a Christian Näther,a Jan van Leusen,b Ulrike Warzok,c Christoph A. Schalley,c Paul Kögerler*b and Wolfgang Bensch*a Minimal-nuclearity vanadato-tungstate clusters in [{VIV(dien)}4- WVI2 O14]·4H2O (1) and [{V IV(dien)}4W VI 4 O20]·6H2O (2) feature cores of edge-sharing WO6 octahedra, surrounded by a ring of four vanadyl groups. Surprisingly, the V(IV) centers in both 1 and 2 are ferro- magnetically coupled, in contrast to all other known vanadato- polyoxotungstates featuring the ubiquituos V–O–W–O–V exchange pathways. The chemistry of mixed-metal polyoxometalates has witnessed an impressive development during the last few decades, with synthetic and structural aspects, properties and possible appli- cations summarized in several review articles.1 The first mixed V–W polyanions were reported already in the 19th century;2 efficient synthesis protocols were developed for the Lindqvist- type polyanions [VxW6−xO19] −2−x (x = 1, 2),3 the solution stabi- lity of which is strongly pH dependent.4 The chemistry of mixed tungstato-vanadate compounds was further developed, resulting primarily in several compounds containing {VxW6−x} (x = 1–3) Lindqvist anions, where V and W atoms usually are disordered over all six metal sites.5 Few other small W/V com- plexes are known with N- and O-donor ligand environments: in [L′O(H2O)V IV(μ-O)WVIO2L] 2+ (L = 1,4,7-triazacyclononane, L′ = 1,4,7-trimethyl-L), VN3O2 and WN3O2 moieties are µ-oxo- bridged,6 in [V2O2(μ-OMe)2(μ-WO4)2(4,4′-di-tert-butyl-2,2′-bi- pyridine)2], two VN2O3 units are bridged by two WO4 groups. 7 After identifying a {V13W4}-type extended Keggin structure under solvothermal conditions at high pH (ca. 12) in the pres- ence of tris(2-aminoethyl)amine (tren),8 we now were able to isolate [(V(dien))4W2O14]·4H2O (1) and [(V(dien))4W4O20]·6H2O (2) (dien = diethylenetriamine, C4H13N3) under similar con- ditions, where a higher reactant V : W ratio (1 : 3 vs. 1 : 4) appears to favor a smaller W nuclearity.‡ The crystal structures feature rare VN2O4 and VN3O3 moieties interconnected by edge-sharing WO6 octahedra (Fig. 1). Compound 1 crystallizes in the triclinic space group P1̄ (Table S1†) with all atoms located on general positions. A W2O10 core composed of two edge-sharing WO6 octahedra con- nects to two VON2 moieties (vanadyl-bidentate diene com- plexes) via three µ-O sites, and edge-sharing to two VON3 units (vanadyl-tridentate fac-dien complexes). The four V sites form a planar rhomboid (V⋯V: 3.78 Å and 5.38 Å, V–V–V: 70.8°). The N⋯N distances in the VN3O3 octahedron are 2.732, 2.714, and 3.278 Å, and the N–N–N angle amounts to 74°. Vanadium dien complexes are rare, with only two corresponding entries, all of tridentate fac conformation, in the CSD.9 In 1, V–N bonds in VN2O4 and VN3O3 (2.116(4)–2.289(4) Å) exhibit a slight elongation of one V–N bond (V1–N2, Fig. S1†), caused by the trans effect. The V–O bonds (1.620(3)–2.219(3) Å) show the typical short vanadyl VvO bonds (1.633(4) and 1.620(3) Å). A database analysis (CSD) of compounds containing octahedral VN2O4 or VN3O3 units yielded a slightly smaller mean value around 1.600 Å. The W–O bonds fall into four groups: 1.752(3) Å (Oterm), 1.824(3)–1.910(3) Å (μ2-O), 2.052(3) Å (μ3-OWV2), and 2.356(3) Å (μ3-OW2V), all typical for polyoxotungstates. In 1, Fig. 1 Combined polyhedral/ball-and-stick plots of the cluster mole- cules in 1 (a) and 2 (b). WO6: grey octahedra, O: red, N: blue, C: black, V: yellow spheres. Terminal VvO vanadyl bonds are emphasized in red. H positions omitted for clarity. †Electronic supplementary information (ESI) available: Experimental, crystallo- graphical and structural details, optical properties and thermal stability data. CCDC 1475726 and 1475727. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6dt02282k aInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, 24118 Kiel, Germany. E-mail: wbensch@ac.uni-kiel.de bInstitut für Anorganische Chemie, RWTH Aachen University, 52074 Aachen, Germany. E-mail: paul.koegerler@ac.rwth-aachen.de cInstitut für Chemie und Biochemie der Freien Universität, 14195 Berlin, Germany This journal is © The Royal Society of Chemistry 2016 Dalton Trans., 2016, 45, 10519–10522 | 10519 O pe n A cc es s A rt ic le . P ub li sh ed o n 10 J un e 20 16 . D ow nl oa de d on 1 6/ 08 /2 01 6 10 :5 7: 44 . T hi s ar ti cl e is l ic en se d un de r a C re at iv e C om m on s A tt ri bu ti on -N on C om m er ci al 3 .0 U np or te d L ic en ce . View Article Online View Journal | View Issue www.rsc.org/dalton http://crossmark.crossref.org/dialog/?doi=10.1039/c6dt02282k&domain=pdf&date_stamp=2016-06-23 http://creativecommons.org/licenses/by-nc/3.0/ http://creativecommons.org/licenses/by-nc/3.0/ http://dx.doi.org/10.1039/c6dt02282k http://pubs.rsc.org/en/journals/journal/DT http://pubs.rsc.org/en/journals/journal/DT?issueid=DT045026 the [(V(dien))4W2O14] complexes are arranged in stacks along [100] and [001], and the inter-cluster voids are occupied by crystal water molecules. Intra-cluster N–H⋯O and extensive 3D inter-cluster H bonding interactions stabilize the structure. O6term is involved in three relatively strong H bonding con- tacts, which may explain the longer VvO bond, while O7term has only one such contact (Table S2†). Bond valence sum (BVS) calculations yield values of 4.06/4.09 for V1/V2 and 5.93 for the unique W atom, in line with the formal oxidation states V4+ and W6+ in 1. Compound 2 crystallizes in the monoclinic space group P21/n (Table S1†) with all unique atoms being located on general positions. Here, the cluster core consists of four edge- sharing WO6 octahedra, forming a distorted W4O4 cubane. Four independent vanadyl groups each bind to a tridentate dien ligand in fac conformation and to two O atoms of neigh- boring WO6 octahedra, resulting in distorted VN3O3 octahedral environments, with two shorter (2.127(7)–2.175(7) Å) and one longer (2.263(5)–2.318(7) Å) V–N bond, the latter trans to the terminal vanadyl O site. The resulting V4 structure is an approximately planar square (V⋯V: 5.94–6.22 Å, root mean square deviation from ideal plane: 0.276 Å). The V–O bonds are similar to those in 1 with one short (1.610(6)–1.628(6) Å, VvOterm) and two longer bonds. The W–O bonds exhibit an identical pattern as in 1. BVS values (V: 3.97–4.17; W: 5.95–6.09) support the proposed oxidation states. In 2, the charge-neutral clusters are arranged in the (010) plane generating channels along [010]. A similar arrangement is observed in the (100) plane, and a second channel type runs along [100]. As in 1, neighbored clusters are interlinked by N– H⋯O interactions, in addition to extensive H bonding to the crystal water molecules present in these channels. The magnetic properties of 1 and 2 are represented in Fig. 2 as χmT vs. T and Mm vs. B plots. For 1, the ambient tempera- ture (290 K) value of χmT is 1.50 cm 3 K mol−1 at 0.1 T. This value lies within the range 1.36–1.53 cm3 K mol−1 expected for four non-interacting VIV centers. Upon cooling χmT continu- ously increases up to a maximum of 1.74 cm3 K mol−1 at 14 K, and subsequently drops off sharply down to 0.77 cm3 K mol−1 at 2.0 K. At 2.0 K, the molar magnetization Mm as a function of the applied field B shows an inflection point at ca. 2.5 T reveal- ing the presence of minor antiferromagnetic exchange inter- actions (the inflection point here indicates a change of the total spin ground state). Modeling the magnetic properties of 1 utilized the computational framework CONDON, employing a “full model” Hamiltonian,10 and assumed four identical V(IV) centers in a C4v-symmetric ligand field, reflecting the pro- nounced tetragonal distortion typical for vanadyl groups. Five Heisenberg-type exchange interaction pathways between nearest-neighbor V(IV) sites (Fig. 2, inset) are characterized by three independent exchange parameters J1 (V–O–V and V–O– WVI–O–V), J2 (V–O–W VI–O–V) and J3 (2 × V–O–W VI–O–V). The O–WVI–O bridges here efficiently mediate the coupling via the extended, unoccupied W 6d orbitals. For fitting purposes, the standard spin–orbit coupling constant ζ3d = 248 cm −1 is taken as a constant,11 and all 10 states of a 3d1 electron configur- ation are accounted for in the calculation of single ion (vanadyl) effects and Heisenberg exchange interactions (“−2J” notation), i.e. considering in total 104 states. Finally, we con- sider the mean-field approach for potential inter-molecular interactions in the solid-state lattice. The least-squares fit (rela- tive root mean squared error, SQ = 1.7%) yields the ligand field parameters (Wybourne notation) B20 = 4230 cm −1, B40 = 23 250 cm−1, B44 = 31 310 cm −1, the exchange interaction para- meters J1 = +15.6 cm −1, J2 = –3.7 cm −1, J3 = +5.9 cm −1, and the mean-field interaction parameter zJ′ = +0.1 cm−1. The ligand field parameters Bkq describe a ligand field characterized by strong tetragonal distortion generating a well-isolated Kramer’s ground state doublet separated from the first excited state by more than 4000 cm−1, reconfirming the almost spin- like behavior of the vanadyl groups. The exchange interaction parameters show predominant ferromagnetic exchange, and the additional antiferromagnetic exchange pathways yields a ground state characterized by Stotal = 0, slightly separated (approx. 2 cm−1) from the first excited Stotal = 1 state, translat- ing into Mm ≈ 2.0NAµB as reflected by the inflection point in Fig. 2 Magnetic data of compounds 1 (top) and 2 (bottom), and coup- ling schemes. χmT vs. temperature T at 0.1 T; insets: molar magnetization Mm vs. applied field B at 2.0 K. Open circles: experimental data, red solid lines: least-squares fit. Communication Dalton Transactions 10520 | Dalton Trans., 2016, 45, 10519–10522 This journal is © The Royal Society of Chemistry 2016 O pe n A cc es s A rt ic le . P ub li sh ed o n 10 J un e 20 16 . D ow nl oa de d on 1 6/ 08 /2 01 6 10 :5 7: 44 . T hi s ar ti cl e is l ic en se d un de r a C re at iv e C om m on s A tt ri bu ti on -N on C om m er ci al 3 .0 U np or te d L ic en ce . View Article Online http://creativecommons.org/licenses/by-nc/3.0/ http://creativecommons.org/licenses/by-nc/3.0/ http://dx.doi.org/10.1039/c6dt02282k the Mm vs. B curve. Inter-cluster interactions are almost negligible. The low-field χmT value of 2 at 290 K of 1.45 cm 3 K mol−1 falls into the expected range for four non-interacting VIV centers. Upon cooling χmT increases sharply below ca. 50 K, reaching 3.57 cm3 K mol−1 at 2.0 K. At 2.0 K, Mm is linear in B up to 1 Tesla, and indicates saturation for fields larger than 5 T at approximately Mm = 4NAμB, i.e. pointing to an Stotal = 2 ground state, i.e. in line with dominant ferromagnetic exchange interactions in 2. In analogy to the analysis of 1 except for the coupling scheme (four V–O–W–O–V pathways characterized by a single exchange energy J), the least-squares fit (SQ = 3.2%) yields B20 = 120 cm −1, B40 = 30 630 cm −1, B44 = 29 460 cm−1, J = +2.7 cm−1, and the mean-field interaction parameter zJ′ = +0.1 cm−1. As for 1, the ligand field parameters here correspond to a strong tetragonal distortion of the V ligand field, generating a well-isolated (ca. 6000 cm−1) Kramer’s ground state doublet. Note that the common V coordination geometry in 2 is significantly different from 1 (two slightly different site geometries), resulting in different ligand field parameters. The positive J reveals small ferro- magnetic nearest-neighbor coupling in 2. The ground state of 2 amounts to Stotal = 2, consistent with the observed saturation value of Mm ≈ 4.0NAμB. As for 1, inter-cluster coupling in 2 is almost negligible. Compound 2 is soluble in water (0.24 mmol L−1), while the solubility of 1 is extremely low. Positive-mode electrospray ionization of a 100 µM water solution of 2 results in an ESI mass spectrum exhibiting the intact cluster as the singly and doubly protonated species at m/z = 836 und 1672 (Fig. 3). The base peak of the spectrum can be assigned to [(V(dien))4W4O19] 2+ which is most likely formed by elimination of H2O upon protonation of the cluster. Measurements were performed shortly after preparation of the sample solution in degassed H2O as the cluster complex was only stable in solu- tion over a period of 30 minutes. In summary, we infer from the two title compounds that the molecular growth of polyoxotungstates at pH ca. 12 appears to be impeded by coordination of VO(dien)2+ groups and the associated decrease in negative molecular charge, effectively stopping at {V4W2} and {V4W4} nuclearities. Com- parison to species formed at similar conditions such as the {V13W4}-type polyanion emphasizes the crucial role of the employed polyamines. These clusters are among the smallest known heterometal polyoxometalates and as such demonstrate the utility of polydentate ligands such as dien in the isolation of novel polyoxometalates structures. To our great surprise, the resulting exchange pathway geometries allow for ferromagnetic coupling between neighboring vanadyl groups, in stark contrast to the usually strongly antiferromagnetic coupling present in larger vanadato-polyoxometalates featuring similar VIV–O–MVI– O–VIV motifs such as the {MVI72V30} Keplerate polyanions. 12 Notes and references ‡Reaction of 1 mmol NH4VO3 and 3 mmol WO3·H2O in a mixture of 2 mL con- centrated diethylentriamine and 2 mL water in a sealed glass tube at 130 °C afforded green rod-shaped crystals of 1 after 7 d (70% yield based on V). Orange block-shaped crystals of 2 formed under otherwise identical conditions with 1 mmol NH4VO3 and 4 mmol WO3·H2O (60% yield based on V). CCDC 1475726 (1) and 1475727 (2). 1 (a) O. Oms, A. Dolbecq and P. Mialane, Chem. Soc. Rev., 2012, 41, 7497; (b) K. Y. Monakhov, W. Bensch and P. Kögerler, Chem. Soc. Rev., 2015, 44, 8443; (c) A. Proust, R. Thouvenot and P. Gouzerh, Chem. Commun., 2008, 1837; (d) A. Müller, P. 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Zhou, Fig. 3 ESI-Q-TOF-HRMS spectrum of compound 2 (100 µM in H2O, top); experimental isotopic pattern of dication at m/z 827 and calculated isotopic pattern of [(V(dien))4W4O19] 2+. Dalton Transactions Communication This journal is © The Royal Society of Chemistry 2016 Dalton Trans., 2016, 45, 10519–10522 | 10521 O pe n A cc es s A rt ic le . P ub li sh ed o n 10 J un e 20 16 . D ow nl oa de d on 1 6/ 08 /2 01 6 10 :5 7: 44 . T hi s ar ti cl e is l ic en se d un de r a C re at iv e C om m on s A tt ri bu ti on -N on C om m er ci al 3 .0 U np or te d L ic en ce . View Article Online http://creativecommons.org/licenses/by-nc/3.0/ http://creativecommons.org/licenses/by-nc/3.0/ http://dx.doi.org/10.1039/c6dt02282k C. Zhong and M. Ji, Cryst. Res. Technol., 2006, 41, 874; (g) C. Wang, L. Weng, Y. Ren, C. Du, B. Yue, M. Gu and H. He, Z. Anorg. Allg. Chem., 2011, 637, 472; (h) Y. Xu, J.-Q. Xu, G.-Y. Yang, T.-G. Wang, Y. Xing, Y.-H. Lin and H.-Q. Jia, Acta Crystallogr., Sect. C: Cryst. 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Communication Dalton Transactions 10522 | Dalton Trans., 2016, 45, 10519–10522 This journal is © The Royal Society of Chemistry 2016 O pe n A cc es s A rt ic le . P ub li sh ed o n 10 J un e 20 16 . D ow nl oa de d on 1 6/ 08 /2 01 6 10 :5 7: 44 . T hi s ar ti cl e is l ic en se d un de r a C re at iv e C om m on s A tt ri bu ti on -N on C om m er ci al 3 .0 U np or te d L ic en ce . View Article Online http://creativecommons.org/licenses/by-nc/3.0/ http://creativecommons.org/licenses/by-nc/3.0/ http://dx.doi.org/10.1039/c6dt02282k Button 1: