Spontaneous Resolution of Chiral Janus-Type Double-Layered Metallocyclic Strips Incorporating Möbius Ring and Circular Helicate.

Homochiral metal-organic macrocyclic complexes are of great significance owing to their chirality and well-defined internal cavities that potentially have the ability to mimic complicated biological processes. Here we report a novel metal/anion-coordination co-driven strategy for the formation of nanoscale supramolecular metallocycles with unique topology, large size, and desired chirality. The enantiomeric Janus-type metallocyclic strips are assembled based on the synergistic coordination of sulfate anions and CoII ions to a bifunctional achiral ligand combining the o-phenylene-(bis)urea anion-chelating and 8-hydroxyquinoline metal-coordinating sites. The inherent chirality arises from two types of helical chiralities (triply twisted Möbius ring and circular helicate), which is observed for the first time for metal-organic complex systems. Notably, spontaneous chiral resolution by conglomerate crystallization into a pair of enantiomers (P- or M-Co9) is realized, which is attributed to the multiple weak intermolecular interactions facilitating the hierarchically helical superstructure.

[1]  Biao Wu,et al.  Anion-Coordination-Driven Assembly. , 2022, Accounts of chemical research.

[2]  J. Holstein,et al.  A Charge-Neutral Self-Assembled L2Zn2 Helicate as Bench-Stable Receptor for Anion Recognition at Nanomolar Concentration. , 2022, Journal of the American Chemical Society.

[3]  P. Peluso,et al.  Recognition in the Domain of Molecular Chirality: From Noncovalent Interactions to Separation of Enantiomers. , 2022, Chemical reviews.

[4]  Quanjie Lin,et al.  Metallo-Supramolecular Octahedral Cages with Three Types of Chirality towards Spontaneous Resolution. , 2022, Angewandte Chemie.

[5]  Biao Wu,et al.  Reversible [4 + 2] Photooxygenation in Anion-Coordination-Driven-Assembled A2L2-Type Complexes. , 2022, Inorganic chemistry.

[6]  Jiacheng Zhang,et al.  Spontaneous Resolution of Racemic Cage-Catenanes via Diastereomeric Enrichment at the Molecular Level and Subsequent Narcissistic Self-Sorting at the Supramolecular Level. , 2022, Journal of the American Chemical Society.

[7]  C. Tung,et al.  Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level , 2021, Nature Communications.

[8]  Yan Liu,et al.  Supramolecular Chirality in Metal-Organic Complexes. , 2020, Accounts of chemical research.

[9]  Feihe Huang,et al.  Formation of Planar Chiral Platinum Triangles via Pillar[5]arene for Circularly Polarized Luminescence. , 2020, Journal of the American Chemical Society.

[10]  Shuangquan Zang,et al.  Spontaneous Resolution of Chiral Multi-Thiolate-Protected Ag30 Nanoclusters , 2020, ACS central science.

[11]  Wenyao Zhang,et al.  Site-Selective Binding of Peripheral Chiral Guests Induces Stereo-specificity in A4L6 Aniono Tetrahedral Cages. , 2020, Journal of the American Chemical Society.

[12]  D. Chand,et al.  Linear and circular helicates: A brief review , 2018, Journal of Chemical Sciences.

[13]  T. Kawai,et al.  Ligand-to-Ligand Interactions That Direct Formation of D2-Symmetrical Alternating Circular Helicate. , 2018, Journal of the American Chemical Society.

[14]  Dan Li,et al.  Self-Assembly of Chiral Metal-Organic Tetartoid. , 2018, Journal of the American Chemical Society.

[15]  K. Rissanen,et al.  Spontaneous Resolution of an Electron-Deficient Tetrahedral Fe4L4 cage. , 2015, Angewandte Chemie.

[16]  K. Rissanen,et al.  Superchiral Pd3 L6 Coordination Complex and Its Reversible Structural Conversion into Pd3 L3 Cl6 Metallocycles. , 2015, Angewandte Chemie.

[17]  Timothy R. Cook,et al.  Self-Assembly of Chiral Metallacycles and Metallacages from a Directionally Adaptable BINOL-Derived Donor. , 2015, Journal of the American Chemical Society.

[18]  Tianyu Wang,et al.  Supramolecular Chirality in Self-Assembled Systems. , 2015, Chemical reviews.

[19]  R. Faulkner,et al.  Formation of a dimer of trinuclear helicates which encapsulates an array of six hydrogen-bonded anions. , 2014, Angewandte Chemie.

[20]  Yang-guang Li,et al.  Polyoxometalate-Induced New Self-Assemblies Based on Copper Ions and Bichelate-Bridging Ligands , 2013 .

[21]  Biao Wu,et al.  Tris chelating phosphate complexes of bis(thio)urea ligands. , 2013, Inorganic chemistry.

[22]  Song Gao,et al.  Zero-field slow magnetic relaxation from single Co(II) ion: a transition metal single-molecule magnet with high anisotropy barrier , 2013 .

[23]  Chaok Seok,et al.  Pulsating Tubules from Noncovalent Macrocycles , 2012, Science.

[24]  T. Bürgi,et al.  First enantioseparation and circular dichroism spectra of Au38 clusters protected by achiral ligands , 2012, Nature Communications.

[25]  Fengping Xiao,et al.  Polyoxometalatocyclophanes: controlled assembly of polyoxometalate-based chiral metallamacrocycles from achiral building blocks. , 2010, Journal of the American Chemical Society.

[26]  M. Albrecht,et al.  8-Hydroxyquinolines in metallosupramolecular chemistry , 2008 .

[27]  Wenbin Lin,et al.  Chiral metallocycles: rational synthesis and novel applications. , 2008, Accounts of chemical research.

[28]  C. Hong,et al.  A chiral pentadecanuclear metallamacrocycle with a sextuple twisted Möbius topology. , 2007, Journal of the American Chemical Society.

[29]  J. Nitschke Construction, substitution, and sorting of metallo-organic structures via subcomponent self-assembly. , 2007, Accounts of chemical research.

[30]  S. Telfer,et al.  Boxes, helicates, and coordination polymers: a structural and magnetochemical investigation of the diverse coordination chemistry of simple pyridine-alcohol ligands. , 2006, Inorganic chemistry.

[31]  Yi-zhi Li,et al.  A chiral luminescent Au16 ring self-assembled from achiral components. , 2005, Journal of the American Chemical Society.

[32]  Mario Ruben,et al.  Grid-type metal ion architectures: functional metallosupramolecular arrays. , 2004, Angewandte Chemie.

[33]  P. Stang,et al.  Self-Assembly, Symmetry, and Molecular Architecture: Coordination as the Motif in the Rational Design of Supramolecular Metallacyclic Polygons and Polyhedra , 1997 .

[34]  J. Lehn,et al.  Self‐Assembly, Structure, and Spontaneous Resolution of a Trinuclear Triple Helix from an Oligobipyridine Ligand and NiII Ions , 1993 .

[35]  M. Fujita,et al.  Metal-directed self-assembly of two- and three-dimensional synthetic receptors , 1998 .