Juan M. Gutiérrez-Zorrilla, Santiago Reinoso, Leire San Felices, Amaia Iturrospe, Pablo Vitoria, Beñat Artetxe, Aroa Pache, Saioa Aguado, and Jagoba Martín Department of Inorganic Chemistry , Faculty of Science and Technology, UPV/EHU, P. O. 644, 48080 Bilbao. Polyoxometalates (POMs): Inorganic Building Blocks for Smart Materials BLACKBERRY FORMATION LANTHANIDE-CONTAINING POMs 3d/4f HETEROMETALLIC POLYOXOMETALATES Ni nickel 28 Co cobalt 27 NaAc + Ce 4+ M 4 (XW 9 ) 2 H 2 O Hexamer Tetramer La Lanthanum Ce Cerium Pr Praseodymiun Self- Assembly Nd Neodymiun Eu Europium Sm Samarium Gd Gadolinium Ho Holmium Tb Terbium Dy Dysprosium Yb Ytterbium Er Erbium Tm Thulium Lu Lutetium 57 58 59 60 63 62 64 66 67 65 68 69 70 71 Unprecedented γ-{Ln 2 GeW 10 } {K⊂(Ln 2 GeW 10 ) 6 } core Zn zinc 30 Cu copper 29 + Ln 3+ NaAc Ln 3 {M(Ac)}Sb 4 (SbW 9 ) 3 (MW 9 ) Ce(Ac)M 3 (XW 9 ) 2 Ce 2 M 2 (XW 9 ) 2 M 2 (Sb 2 W 20 ) [Cu(cyclam)] 2 [{α- GeW 11 O 39 RE(H 2 O)(μ-ac ac )} 2 {Cu(cyclam} 4 ]. nH 2 O RE: La, Sm, Eu, Gd, Tb, Dy, Ho, Er POMs FOR SMART SENSORS Dimer Dodecamer H 2 O Dissociation H 2 O Dissociation H 2 O Dissociation -H2O + H2O Cu1A Cu1B Cu1A Cu1B Financial support Gobierno Vasco (IT-477-10); UFI 11/53. SINGLE-CRYSTAL TO SINGLE-CRYSTAL (SCSC) TRANSFORMATION CRYSTAL STRUCTURE TRANSFORMATION TRANSFORMATION OF HYBRID POMs a c e b d Polystyrene-b-poly(acrylyc acid) BREATH FIGURE SURFACE FORMATION FOR POM ANCHORING TGA-DTA/PXRD +H 2 O +H 2 O ∆ -H 2 O + H 2 O -H 2 O + H 2 O -H 2 O