United Complexes or [2]Catenanes: Curvature-Controlled Cooperative π-Coordination Mimicking θ-Curve Motifs
Abstract
Control over the solid-state self-assembly of (M 3 L 2 ) 2 -type entangled complexes (M = Cuᴵ, Agᴵ) and interlocked [2]catenanes was achieved through structural modification of the curved tripodal arms of triarylmethane-based ligands (L). When 3-pyridyl groups served as terminal coordination donors on appropriately curved tripodal arms, cooperative metal–acetylene π-coordination, reminiscent of the secondary cross-linking found in nontrivial θ -curve motifs of entangled proteins, generated additional intercomponent connectivity and bridged the two M 3 L 2 cages to form a “united” complex. In contrast, incorporation of 4-pyridyl donors reduced the curvature of the tripodal arms and afforded a normal [2]catenane lacking such inter-cage cross-linking. Furthermore, insertion of an m -phenylene–ethynylene spacer produced a unique dissymmetric [2]catenane in the crystalline state. These results demonstrate that subtle changes in ligand geometry can regulate secondary connectivity while preserving the underlying (M 3 L 2 ) 2 entangled framework, thereby providing access to distinct interlocked architectures. The introduction and control of θ -curve-like secondary linkages thus offer a new design principle for coordination-driven nanostructures based on molecular entanglement.
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BibTeX
@misc{domoto2026united,
title = {{United Complexes or [2]Catenanes: Curvature-Controlled Cooperative π-Coordination Mimicking θ-Curve Motifs}},
author = {Yuya Domoto and Masaya Kobayashi and Shumpei Horie and Masahiro Abe and Kidai Yamamoto and Tasuki Tsurumi and Hironobu Hayashi and Yosuke Nakamura and Makoto Fujita},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009544/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009544/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - United Complexes or [2]Catenanes: Curvature-Controlled Cooperative π-Coordination Mimicking θ-Curve Motifs
AU - Yuya Domoto
AU - Masaya Kobayashi
AU - Shumpei Horie
AU - Masahiro Abe
AU - Kidai Yamamoto
AU - Tasuki Tsurumi
AU - Hironobu Hayashi
AU - Yosuke Nakamura
AU - Makoto Fujita
PY - 2026
DA - 2026/09/28
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009544/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009544/v1
AB - Control over the solid-state self-assembly of (M 3 L 2 ) 2 -type entangled complexes (M = Cuᴵ, Agᴵ) and interlocked [2]catenanes was achieved through structural modification of the curved tripodal arms of triarylmethane-based ligands (L). When 3-pyridyl groups served as terminal coordination donors on appropriately curved tripodal arms, cooperative metal–acetylene π-coordination, reminiscent of the secondary cross-linking found in nontrivial θ -curve motifs of entangled proteins, generated additional intercomponent connectivity and bridged the two M 3 L 2 cages to form a “united” complex. In contrast, incorporation of 4-pyridyl donors reduced the curvature of the tripodal arms and afforded a normal [2]catenane lacking such inter-cage cross-linking. Furthermore, insertion of an m -phenylene–ethynylene spacer produced a unique dissymmetric [2]catenane in the crystalline state. These results demonstrate that subtle changes in ligand geometry can regulate secondary connectivity while preserving the underlying (M 3 L 2 ) 2 entangled framework, thereby providing access to distinct interlocked architectures. The introduction and control of θ -curve-like secondary linkages thus offer a new design principle for coordination-driven nanostructures based on molecular entanglement.
ER -