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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

    Molecular self-assembly is controlled by chemical and entropic factors, but theory has not been able to differentiate the role of each. Here, the authors unambiguously address this question for self-assembly on metal surfaces, using a new computational method that bridges coarse-grained and atomistic approaches.

    • Daniel M. Packwood
    • , Patrick Han
    •  &  Taro Hitosugi
  • Nature Communications | Article | open

    Understanding the dynamics of supramolecular architectures without using labels is crucial for developing advanced biosystems. Here, the authors show kinetic hydrogen/deuterium exchange profiles for a series of water-soluble supramolecular polymers.

    • Xianwen Lou
    • , René P. M. Lafleur
    • , Christianus M. A. Leenders
    • , Sandra M. C. Schoenmakers
    • , Nicholas M. Matsumoto
    • , Matthew B. Baker
    • , Joost L. J. van Dongen
    • , Anja R. A. Palmans
    •  &  E W Meijer

Discrete Assemblies

  • 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

    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

    Under confinement, molecular switches lose the conformational freedom often needed to isomerize. Here, the authors show that a flexible coordination cage can adapt its shape to guide the photoisomerization of encapsulated spiropyrans, rendering them reversibly photochromic even within the confines of the cavity.

    • Dipak Samanta
    • , Daria Galaktionova
    • , Julius Gemen
    • , Linda J. W. Shimon
    • , Yael Diskin-Posner
    • , Liat Avram
    • , Petr Král
    •  &  Rafal Klajn
  • Nature Communications | Article | open

    The complex, multicomponent structures often found in nature are difficult to mimic synthetically. Here, the authors assemble a molecular analogue of a peanut through coordinative and π-stacking interactions, in which a polyaromatic double capsule ‘pod’ held together by metal ions encapsulates fullerene ‘beans’.

    • Kohei Yazaki
    • , Munetaka Akita
    • , Soumyakanta Prusty
    • , Dillip Kumar Chand
    • , Takashi Kikuchi
    • , Hiroyasu Sato
    •  &  Michito Yoshizawa
  • Nature Communications | Article | open

    Host—guest assemblies can exploit stimuli-responsive guest binding and release for molecular recognition, but are typically governed by thermodynamics alone. Here, the authors design macrocycles with removable and exchangeable anion caps, allowing for the kinetic trapping and on-demand exchange of guest ions.

    • Yoko Sakata
    • , Chiho Murata
    •  &  Shigehisa Akine
  • Nature Communications | Article | open

    New approaches are required to access metal-organic assemblies with unusual structural properties. Here, the authors use an in situ redox reaction to obtain a mixed-valence, Mn(II)/Mn(III)-containing metal-organic nanocapsule with an odd number of metal ions.

    • Asanka S. Rathnayake
    • , Hector W. L. Fraser
    • , Euan K. Brechin
    • , Scott J. Dalgarno
    • , Jakob E. Baumeister
    • , Joshua White
    • , Pokpong Rungthanaphatsophon
    • , Justin R. Walensky
    • , Charles L. Barnes
    • , Simon J. Teat
    •  &  Jerry L. Atwood

Materials Design

  • 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

    Reaction-diffusion controls the spatial formation of many natural structures but is rarely applied to organic materials. Here, the authors couple reaction-diffusion to the self-assembly of a supramolecular gelator, introducing a strategy to forming soft, free-standing objects with controlled shape and functionality.

    • Matija Lovrak
    • , Wouter E. J. Hendriksen
    • , Chandan Maity
    • , Serhii Mytnyk
    • , Volkert van Steijn
    • , Rienk Eelkema
    •  &  Jan H. van Esch
  • Nature Communications | Article | open

    Polymersomes have become a powerful tool in drug delivery and synthetic biology, but their use can be restricted by a lack of versatile methods for shape control. Here the authors demonstrate access to a range of non-spherical polymersome morphologies by exploiting hydrophobic directional aromatic perylene interactions within the membrane structure.

    • Chin Ken Wong
    • , Alexander F. Mason
    • , Martina H. Stenzel
    •  &  Pall Thordarson
  • Nature Communications | Article | open

    Crystallization-driven processes play a vital role in preparing 2D nanostructures which makes structures with high symmetry hard to access. Here the authors present a non-crystallization approach which is based on π–π interactions of a copolymer for the fabrication of 2D symmetric structures with good dimensional control.

    • Liang Han
    • , Meijing Wang
    • , Xiangmeng Jia
    • , Wei Chen
    • , Hujun Qian
    •  &  Feng He
  • Nature Communications | Article | open

    Achieving precise control of host–guest interactions in artificial systems is difficult. Here the authors use the thermodynamics of a system in equilibrium to control stepwise release and capture of cyclodextrin (guest) using a coordination polymer as the host and temperature as the stimulus.

    • Rahul Dev Mukhopadhyay
    • , Gourab Das
    •  &  Ayyappanpillai Ajayaghosh

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

    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
  • Nature Communications | Article | open

    Molecules that act as both autocatalysts and material precursors offer exciting prospects for self-synthesizing materials. Here, the authors design a triazole peptide that self-replicates and then self-assembles into nanostructures, coupling autocatalytic and assembly pathways to realize a reproducing supramolecular system.

    • Roberto J. Brea
    •  &  Neal K. Devaraj