Nitrile Geometry as an Architectural Code for Cu10 Nanocluster Metal–Organic Frameworks

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.

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BibTeX RIS

BibTeX

@misc{kondo2026nitrile,
  title = {{Nitrile Geometry as an Architectural Code for Cu10 Nanocluster Metal–Organic Frameworks}},
  author = {Ayumu Kondo and Riki Nakatani and Sreelakshmi K. S. and Tsukasa Irie and Yunosuke Arai and Yuya Sugawara and Tokuhisa Kawawaki and Saikat Das and Yuichi Negishi},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008878/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008878/v1},
  note = {CC BY},
}

RIS

TY  - UNPB
TI  - Nitrile Geometry as an Architectural Code for Cu10 Nanocluster Metal–Organic Frameworks
AU  - Ayumu Kondo
AU  - Riki Nakatani
AU  - Sreelakshmi K. S.
AU  - Tsukasa Irie
AU  - Yunosuke Arai
AU  - Yuya Sugawara
AU  - Tokuhisa Kawawaki
AU  - Saikat Das
AU  - Yuichi Negishi
PY  - 2026
DA  - 2026/09/15
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008878/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008878/v1
AB  - 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.
ER  -

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