Site Selectivity for the Spin States and Spin Crossover in Undecanuclear Heterometallic Cyanido-Bridged Clusters

[Image: see text] Polynuclear molecular clusters offer an opportunity to design new hierarchical switchable materials with collective properties, based on variation of the chemical composition, size, shapes, and overall building blocks organization. In this study, we rationally designed and constructed an unprecedented series of cyanido-bridged nanoclusters realizing new undecanuclear topology: Fe(II)[Fe(II)(bzbpen)](6)[W(V)(CN)(8)](2)[W(IV)(CN)(8)](2)·18MeOH (1), Na(I)[Co(II)(bzbpen)](6)[W(V)(CN)(8)](3)[W(IV)(CN)(8)]·28MeOH (2), Na(I)[Ni(II)(bzbpen)](6)[W(V)(CN)(8)](3)[W(IV)(CN)(8)]·27MeOH (3), and Co(II)[Co(II)(R/S-pabh)(2)](6)[W(V)(CN)(8)](2)[W(IV)(CN)(8)](2)·26MeOH [4R and 4S; bzbpen = N(1),N(2)-dibenzyl-N(1),N(2)-bis(pyridin-2-ylmethyl)ethane-1,2-diamine; R/S-pabh = (R/S)-N-(1-naphthyl)-1-(pyridin-2-yl)methanimine], of size up to 11 nm(3), ca. 2.0 × 2.2 × 2.5 nm (1–3) and ca. 1.4 × 2.5 × 2.5 nm (4). 1, 2, and 4 exhibit site selectivity for the spin states and spin transition related to the structural speciation based on subtle exogenous and endogenous effects imposed on similar but distinguishable 3d metal-ion-coordination moieties. 1 exhibits a mid-temperature-range spin-crossover (SCO) behavior that is more advanced than the previously reported SCO clusters based on octacyanidometallates and an onset of SCO behavior close to room temperature. The latter feature is also present in 2 and 4, which suggests the emergence of Co(II)-centered SCO not observed in previous bimetallic cyanido-bridged Co(II)–W(V/IV) systems. In addition, reversible switching of the SCO behavior in 1 via a single-crystal-to-single-crystal transformation during desolvation was also documented.