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Supramolecular Chemistry

Supramolecular chemistry specializes in non-covalent interactions. These weak and reversible forces—such as hydrogen bonds, hydrophobic forces, van der Waals forces, and metal–ligand coordination—are key to understanding biological processes and self-assembling systems, and to constructing complex materials and molecular machinery. In the several decades since its conception, supramolecular chemistry has become a truly interdisciplinary research area, providing insights into and spurring developments across biology, chemistry, nanotechnology, materials science, and physics.

In this collection, we highlight a selection of recent experimental and theoretical studies published in Nature Communications, which we hope reflect the true breadth of supramolecular chemistry as a discipline. The collection features advances in building discrete assemblies and extended material systems, all through the clever design of non-covalently organizing components. We also showcase fundamental research that furthers our understanding of the range of interactions that make up the supramolecular chemist’s toolbox.

Physical Principles

  • Nature Communications | Article | open

    Homo radical spin-pairing interactions between two identical aromatic radicals are common in supramolecular chemistry, but hetero interactions between two different aromatic radicals are seldom observed. Here, the authors find that hetero radical pairing between a radical cation and a radical anion, together with Coulombic attraction, can drive host-guest recognition, representing a new supramolecular recognition motif.

    • Xujun Zheng
    • , Yang Zhang
    • , Ning Cao
    • , Xin Li
    • , Shuoqing Zhang
    • , Renfeng Du
    • , Haiying Wang
    • , Zhenni Ye
    • , Yan Wang
    • , Fahe Cao
    • , Haoran Li
    • , Xin Hong
    • , Andrew C.-H. Sue
    • , Chuluo Yang
    • , Wei-Guang Liu
    •  &  Hao Li
  • Nature Communications | Article | open

    Attractive, non-covalent interactions between aromatic rings—termed ππ stacking—is common in chemistry but difficult to model. Here the authors report a quantum-mechanical model to show the importance of collective charge fluctuations for understanding pi-stacked supramolecular systems.

    • Jan Hermann
    • , Dario Alfè
    •  &  Alexandre Tkatchenko
  • Nature Communications | Article | open

    Deuterating a hydrogen bond can change the bond’s geometry, a phenomenon known as the geometric isotope effect (GIE). Here, the authors find that a hydrogen-bonded host–guest crystal, imidazolium hydrogen terephthalate, exhibits significant GIE on its hydrogen bonds, changing its crystal phases and bulk dielectric properties.

    • Chao Shi
    • , Xi Zhang
    • , Chun-Hua Yu
    • , Ye-Feng Yao
    •  &  Wen Zhang
  • Nature Communications | Article | open

    Hydrogen-bonds are widely found in many systems, such as DNAs and supramolecular assemblies, but it remains challenging to detect their dynamics at a molecular level. Here, Zhou et al. study the stochastic arrangement of hydrogen bonds using single-molecule junctions connected to graphene electrodes.

    • Ce Zhou
    • , Xingxing Li
    • , Zhongliang Gong
    • , Chuancheng Jia
    • , Yuanwei Lin
    • , Chunhui Gu
    • , Gen He
    • , Yuwu Zhong
    • , Jinlong Yang
    •  &  Xuefeng Guo
  • Nature Communications | Article | open

    Complex assembly pathways often involve transient, partly-formed intermediates that are challenging to characterize. Here, the authors present a simple and rapid spectroscopic thermal hysteresis method for mapping the energy landscapes of supramolecular assembly.

    • Robert W. Harkness V
    • , Nicole Avakyan
    • , Hanadi F. Sleiman
    •  &  Anthony K. Mittermaier
  • Nature Communications | Article | open

    Bottom-up fabrication via on-surface molecular self-assembly is a useful way to make nanomaterials, but finding appropriate precursor molecules for a given structure remains a challenge. Here the authors present an informatics technique linking self-assembled structures with precursor properties, helping identify molecules for target nanomaterials.

    • Daniel M. Packwood
    •  &  Taro Hitosugi

Discrete Assemblies

  • Nature Communications | Article | open

    Container-molecules capable of recognizing charged species possess great potential as sensors, but are typically limited by their rigid frameworks. Here, Sun and co-workers design a family of adaptive metal-organic macrocycles that exhibit shape and size induced-fit transformations upon anion-binding.

    • Ting Zhang
    • , Li-Peng Zhou
    • , Xiao-Qing Guo
    • , Li-Xuan Cai
    •  &  Qing-Fu Sun
  • Nature Communications | Article | open

    Hierarchical non-intertwined ring-in-ring complexes are intriguing but challenging supramolecular targets. Here, the authors describe a box-in-box assembly based on radical-pairing interactions between two rigid diradical dicationic cyclophanes; the inner box can further accommodate guests to form Russian doll-like assemblies.

    • Kang Cai
    • , Mark C. Lipke
    • , Zhichang Liu
    • , Jordan Nelson
    • , Tao Cheng
    • , Yi Shi
    • , Chuyang Cheng
    • , Dengke Shen
    • , Ji-Min Han
    • , Suneal Vemuri
    • , Yuanning Feng
    • , Charlotte L. Stern
    • , William A. Goddard III
    • , Michael R. Wasielewski
    •  &  J. Fraser Stoddart
  • Nature Communications | Article | open

    Coordination-driven supramolecular assembly provides the ability to build molecular architectures of impressive complexity. Here, the authors use a series of linear metal-organic ligands with specific sequences to construct multiple generations of precisely-controlled, 2D fractal polycyclic supramolecules.

    • Bo Song
    • , Sneha Kandapal
    • , Jiali Gu
    • , Keren Zhang
    • , Alex Reese
    • , Yuanfang Ying
    • , Lei Wang
    • , Heng Wang
    • , Yiming Li
    • , Ming Wang
    • , Shuai Lu
    • , Xin-Qi Hao
    • , Xiaohong Li
    • , Bingqian Xu
    •  &  Xiaopeng Li
  • Nature Communications | Article | open

    Nested structures are common throughout nature and art, yet remain challenging synthetic targets in supramolecular chemistry. Here, the authors design multitopic terpyridine ligands that coordinate into nested concentric hexagons, and show that these discrete supramolecules display potent antimicrobial activity.

    • Heng Wang
    • , Xiaomin Qian
    • , Kun Wang
    • , Ma Su
    • , Wei-Wei Haoyang
    • , Xin Jiang
    • , Robert Brzozowski
    • , Ming Wang
    • , Xiang Gao
    • , Yiming Li
    • , Bingqian Xu
    • , Prahathees Eswara
    • , Xin-Qi Hao
    • , Weitao Gong
    • , Jun-Li Hou
    • , Jianfeng Cai
    •  &  Xiaopeng Li
  • Nature Communications | Article | open

    Molecular capsules typically bind only guests with volumes smaller than their cavities. Here, the authors find that a polyaromatic capsule accommodates linear amphiphilic oligomers in a length-dependent manner, whereas short chains are fully crammed into the cavity, long chains can be incorporated into the capsule in a threaded fashion.

    • Masahiro Yamashina
    • , Shunsuke Kusaba
    • , Munetaka Akita
    • , Takashi Kikuchi
    •  &  Michito Yoshizawa
  • Nature Communications | Article | open

    Supramolecular containers are promising enzyme mimics, but they currently accommodate only a limited range of chemical transformations. Here, the authors describe coordination cages that catalyze two-component cascade reactions without relying on an external or encapsulated catalytic species.

    • Jingjing Jiao
    • , Zijian Li
    • , Zhiwei Qiao
    • , Xu Li
    • , Yan Liu
    • , Jinqiao Dong
    • , Jianwen Jiang
    •  &  Yong Cui

Materials Design

  • Nature Communications | Article | open

    Molecular tessellations of complex tilings are difficult to design and construct. Here, the authors show that molecular tessellations can be formed from a single building block that gives rise to two distinct supramolecular phases, whose self-similar subdomains serve as tiles in the periodic tessellations.

    • Fang Cheng
    • , Xue-Jun Wu
    • , Zhixin Hu
    • , Xuefeng Lu
    • , Zijing Ding
    • , Yan Shao
    • , Hai Xu
    • , Wei Ji
    • , Jishan Wu
    •  &  Kian Ping Loh
  • Nature Communications | Article | open

    Modulating the structural and transient characteristics of synthetic nanostructures can be achieved by temporal control of supramolecular assemblies. Here the authors show a biomimetic, ATP-selective and fuel-driven controlled supramolecular polymerization of a phosphate receptor functionalised monomer.

    • Ananya Mishra
    • , Divya B. Korlepara
    • , Mohit Kumar
    • , Ankit Jain
    • , Narendra Jonnalagadda
    • , Karteek K. Bejagam
    • , Sundaram Balasubramanian
    •  &  Subi J. George
  • Nature Communications | Article | open

    Dynamically controlling the conformations of 1D elongated supramolecular polymers can induce functions comparable to protein folding/unfolding. Here the authors show light-induced conformational changes of azobenzene-based supramolecular polymers from helically coiled to extended/randomly coiled conformations.

    • Bimalendu Adhikari
    • , Yuki Yamada
    • , Mitsuaki Yamauchi
    • , Kengo Wakita
    • , Xu Lin
    • , Keisuke Aratsu
    • , Tomonori Ohba
    • , Takashi Karatsu
    • , Martin J. Hollamby
    • , Nobutaka Shimizu
    • , Hideaki Takagi
    • , Rie Haruki
    • , Shin-ichi Adachi
    •  &  Shiki Yagai
  • Nature Communications | Article | open

    Nature can precisely control monomer sequences in biopolymers, but this is somewhat problematic in the formation of synthetic polymers. Here the authors show sequence-controlled supramolecular terpolymerization via self-sorting behavior among three sets of monomers possessing mismatched host-guest pairs.

    • Takehiro Hirao
    • , Hiroaki Kudo
    • , Tomoko Amimoto
    •  &  Takeharu Haino
  • Nature Communications | Article | open

    Porosity in metal–organic materials typically relies on highly ordered crystalline networks, which hinders material processing and morphological control. Here, the authors use metal–organic polyhedra as porous monomers in supramolecular polymerization to produce colloidal spheres and gels with intrinsic microporosity.

    • Arnau Carné-Sánchez
    • , Gavin A. Craig
    • , Patrick Larpent
    • , Takashi Hirose
    • , Masakazu Higuchi
    • , Susumu Kitagawa
    • , Kenji Matsuda
    • , Kenji Urayama
    •  &  Shuhei Furukawa
  • Nature Communications | Article | open

    Chirality transfer by chemical self-assembly has been studied intensively for years but chirality transfers along the same path remains elusive. Here the authors use a multiscale chemo-mechanical model to elucidate the mechanism underlying the chirality transfer via self-assembly in hierarchical camphorsulfonic acid doped polyaniline.

    • Yang Yang
    • , Jie Liang
    • , Fei Pan
    • , Zhen Wang
    • , Jianqi Zhang
    • , Kamran Amin
    • , Jin Fang
    • , Wenjun Zou
    • , Yuli Chen
    • , Xinghua Shi
    •  &  Zhixiang Wei

Systems Chemistry

  • Nature Communications | Article | open

    Several cell functions are based on the fuel-driven assembly and disassembly of supramolecular polymers under non-equilibrium conditions. Here, the authors show controlled formation and breaking of a supramolecular polymer by enzymatic phosphorylation and dephosphorylation of a building block by continuously adding ATP fuel and removing waste products.

    • Alessandro Sorrenti
    • , Jorge Leira-Iglesias
    • , Akihiro Sato
    •  &  Thomas M. Hermans
  • Nature Communications | Article | open

    Selection and persistence of chemical non-equilibrium species is crucial for the emergence of life and the exact mechanisms remain elusive. Here the authors show that phase separation is an efficient way to control selection of chemical species when primitive carboxylic acids are brought out-of-equilibrium by high-energy condensing agents.

    • Marta Tena-Solsona
    • , Caren Wanzke
    • , Benedikt Riess
    • , Andreas R. Bausch
    •  &  Job Boekhoven
  • Nature Communications | Article | open

    Unravelling the fundamental mechanisms of emergence of complex behaviour is key to understanding living systems. Here, the authors provide a simple experimental platform to investigate and control a rich set of complex phenomena, akin to those seen in living organisms, from a nonliving system of colloidal nanoparticles.

    • Serim Ilday
    • , Ghaith Makey
    • , Gursoy B. Akguc
    • , Özgün Yavuz
    • , Onur Tokel
    • , Ihor Pavlov
    • , Oguz Gülseren
    •  &  F. Ömer Ilday
  • Nature Communications | Article | open

    Hydrogen bonds are powerful supramolecular motifs, owing to their selective and dynamic nature. Here, the authors build orthogonal hydrogen-bonding sites into a single molecule, allowing it to form diverse hierarchical assemblies and exhibit self-sorting behaviour in response to certain stimuli.

    • Qixun Shi
    • , Tomas Javorskis
    • , Karl-Erik Bergquist
    • , Artūras Ulčinas
    • , Gediminas Niaura
    • , Ieva Matulaitienė
    • , Edvinas Orentas
    •  &  Kenneth Wärnmark
  • Nature Communications | Article | open

    Understanding self-replication and persistence in an out-of-equilibrium state is key to designing systems with new properties mimicking “living systems”. Here, the authors developed a synthetic small molecule system in which a transient surfactant replicator is responsible for both an autocatalytic aggregation pathway and a destructive pathway.

    • Ignacio Colomer
    • , Sarah M. Morrow
    •  &  Stephen P. Fletcher
  • Nature Communications | Article | open

    Coupling compartmentalisation and molecular replication is essential for the development of evolving chemical systems. Here the authors show an oil-in-water droplet containing a self-replicating amphiphilic imine that can undergo repeated droplet division.

    • J. W. Taylor
    • , S. A. Eghtesadi
    • , L. J. Points
    • , T. Liu
    •  &  L. Cronin