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

The two first representatives of phthalocyaninato (Pc) lanthanide-ligated polyoxovanadate cages {[V12O32(Cl)](LnPc)n}n-5 (n = 1 or 2, Ln = Yb3+) were synthesised and fully characterised. These magnetic complexes form two-dimensional self-assembled monolayers exhibiting electrical conductivity on gold substrate surfaces, as assessed by using an EGaIn tip

Phosphorus or nitrogen – the first phosphatriptycene in coordination polymer chemistry

Phosphasilatriptycene, a phenylene spacer and a pyridyl moiety represent the building blocks of TRIP-Py, the first heteroditopic ligand featuring a phoshatriptycene scaffold. The P and N donor sites located at opposite ends of the prolate TRIP-Py molecule selectively coordinate metal cations matching their Pearson character. The harder pyridyl donor binds to ZnII, the softer phosphorus donor to PtII, HgII and AuI. The remarkably short Au–P bond in the latter underlines the good π acceptor character of the phoshatriptycene moiety. When both the chloride salts of hard ZnII and soft AuI cations are available for coordination, TRIP-Py acts as selective ditopic linker in the discrete trinuclear mixed-metal complex [ZnCl2(TRIP–PyAuCl)2]. For CdII, a cation with intermediate Pearson character, selectivity withers, and a monometallic coordination polymer is obtained. Its significantly elongated Cd–P coordinative bonds underline, however, the preference of CdII for the harder N donor. When ZnII and HgII halides are combined, their preference for the matching donor sites in TRIP-Py and for tetrahedral coordination afford 1D and 2D heterobimetallic polymers with and without solvent-accessible voids. TRIP-Py enables the use of two important analytical tools: its rigidity facilitates crystallization and allowed to investigate 14 crystalline solids, and its P donor provides a powerful NMR probe for coordination

CCDC 1950768: Experimental Crystal Structure Determination

Related Article: Ricarda Pütt, Xinkai Qiu, Piotr Kozłowski, Hans Gildenast, Oliver Linnenberg, Stefan Zahn, Ryan C. Chiechi, Kirill Yu. Monakhov|2019|Chem.Commun.|55|13554|doi:10.1039/C9CC06852