Year: 2026
Type: preprint
Abstract: Atomically precise nanoclusters offer molecularly defined metal architectures, yet their conversion into extended frameworks remains difficult because reticulation must impose long-range order without erasing the structural adaptability of the multinuclear node. Here, we show that nitrile geometry can function as an architectural code for Cu10 nanocluster metal–organic frameworks (NCMOFs). Rather than relying on conventional pyridyl donors, we employ sterically minimal aryl nitriles whose weaker donor character is coupled to sharply defined coordination vectors. Natural population analysis confirms that nitrile N atoms are substantially less electron-rich than representative pyridyl donors, establishing a distinct electronic regime for cluster reticulation. Using terephthalonitrile (TPN), isophthalonitrile (IPN), and 1,3,5-tricyanobenzene (TCB), we obtain four crystallographically distinct frameworks— Cu10TPN-1D, Cu10IPN-2D, Cu10IPN-1D, and Cu10TCB-2Dthrough diffusion-controlled assembly of a common Cu–thiolate precursor. Single-crystal structures reveal that the Cu–N interface remains comparatively constrained, while Cu···Cu, Cu–S, and especially Cu–O metrics reorganize to accommodate different linker vectors and lattice demands. Strikingly, the same 120° IPN linker yields either 1D or 2D connectivity depending on the crystallization medium, demonstrating that linker geometry defines an accessible connectivity landscape rather than a predetermined topology. These results establish a broader design principle for NCMOFs: directional information can be encoded in a weakly donating linker, while structural compliance is retained within the nanocluster node, enabling adaptive multinuclear units to translate molecular geometry into distinct reticular states.
Source: ChemRxiv
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7213322190