Self-assembled monolayers of polyoxovanadates with phthalocyaninato lanthanide moieties on gold surfaces

Abstract

Conductive self-assembled monolayers of host–guest vanadium–oxo cages functionalised with phthalocyaninato YbIII moieties have been formed on gold surfaces.

Phthalocyanine-polyoxotungstate lanthanide double deckers

“…[35][36][37][38][39][40][41][42][43][44][45] Despite these prospects, there is just one report of a doubledecker Ln III complex comprising both a phthalocyanine and a polyoxometalate, namely a Yb 3+ complex with a polyoxovanadate. 46 In contrast, we here focus on the lanthanide ions Tb 3+ (4f 8 ) and Dy 3+ (4f 9 ) that exhibit especially high magnetic anisotropy in LnPc2-type double decker complexes, 15 in conjunction with a thermodynamically highly stable, classical polyoxotungstate ligand.…”

Molecular Nanocomposites with Lanthanide- and Counter-Cation-Mediated Interfacial Electron Transfer between Phthalocyanine and Polyoxovanadate

“…Monophthalocyanine lanthanide acetate complexes (PcLnOAc) with Ln = Sm III -Er III , Lu III and Y III were synthesised similarly to the protocols described in the literature. 39,27 Repeated purification by column chromatography and subsequent slow evaporation of PcLnOAc•MeOH•H2O in wet ethanol delivered high-quality PcLnOAc•EtOH•H2O crystals for Ln = Sm III , Dy III , Lu III and Y III (see the ESI † ). The synthesis of PcLnOAc with earlier lanthanides (Ln = La III -Nd III ) was not successful likely due to their larger ionic radii.…”

“…Please do not adjust margins Please do not adjust margins according to the synthetic routes developed in our previous Communication 27 for [V12O32Cl(YbPc)n] n−5 with n = 1 or 2 (see the ESI † ). CHN elemental analysis, thermogravimetric (TG) measurements, IR-and UV-Vis-spectroscopy and 1 H NMR spectra (for PcLu-{V12}) of powder samples confirmed the identity and the purity of the synthesised compounds as well as the presence of three and two nBu4N + counter-cations per {V12} in PcLn-{V12} and (PcLn)2-{V12} compounds, respectively (see the ESI † ).…”

“…It might thus be used to tailor electron communication within quantum networks. Secondly, enabling direct interaction between V-POM and LnPc we succeeded 27 in the synthesis of structurally robust, electron correlated compounds [V12O32Cl(YbPc)n] n−5 (n = 1 or 2), in which the dodecavanadate cage is covalently capped by one or sandwiched by two YbPc moieties. Building upon this work, 27 we now report on a broad spectrum of unique chemical physics of [HV12O32Cl(LnPc)n] n−4 compounds for Ln = Sm III -Er III , Lu III and Y III (hereafter referred to as PcLn-{V12} for n = 1 and (PcLn)2-{V12} for n = 2) using a combination of experimental and computational techniques.…”

Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications

“…On the other hand, Kögerler et al disclosed new thermodynamically highly stable phthalocyanine-polyoxotungstate lanthanide double deckers, in which the redox-active polyoxometalates serve as versatile polydentate ligands; 378 multiple decker-like phthalocyaninato lanthanide-ligated polyoxovanadate cages {[V 12 O 32 (Cl)](YbPc) x } nÀ5 (x = 1 or 2) have also been synthesized and characterized. 379 Given the cornucopias of polyoxometalate structures, we believe that developing various functional lanthanidetetrapyrrole-polyoxometalates with improved optical and redox properties and optimizing them for unparalleled photonic and biomedical applications will become an attractive research direction in this field.…”