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Responsive Molecular Systems through Dynamic Covalent Chemistry
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Organic chemistry.ORCID iD: 0000-0001-8020-0579
2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nature tends to inspire research in chemistry. Systems that emerge from molecules interacting via reaction networks is something that life has mastered over the course of evolution in order to produce complexity. Dynamic reactions are key in systems chemistry, where reaction networks give rise to complex, emergent behavior. This thesis aims to harness a special feature of selected dynamic reaction systems – responsiveness.The first chapter of this thesis introduces dynamic covalent chemistry and a general approach to create simple reaction networks by connecting dynamic covalent reactions. Concepts in systems chemistry are introduced in terms of network topology, responsiveness and non-equilibrium processes, while drawing parallels to natural systems.The second chapter explores the potential of the nitroaldol reaction for dynamic systems. Nitroaldol reactions are demonstrated for dynamic polymerization as well as formaldehyde-responsive breakdown of dynamic polymers. The simultaneous formation and breakdown of polymers create emergent non-equilibrium behavior. Furthermore, nitroaldol produced-diols are used in boronate ester formation. This reactivity produces interdependence over two reactions. Combining nitroaldol and boronate building blocks enabled boronate dynamers of different topology.The third chapter explores metal coordination effects in dynamic reaction networks. Novel base-free nitroaldol reactivity is exploited in reaction networks with hemiacetals. A systemic response to metals is demonstrated by hemiacetal-metal coordination. In the second half of the chapter, a biomimetic dynamic imine complex is shown to produce emergent, π-π-interactions resembling a “draw-bridge”. Variation of metal charge, effective electrostatic character of substituent and ligands gives control over the system and its emergent π-π-interactions.

Abstract [sv]

Naturen tenderar att inspirera forskning inom kemi. System uppkommer från molekyler som interagerar i reaktionsnätverk, något som levande system genom hundratusentals år av evolution har utnyttjat för att producera ständigt växande komplexitet. Dynamiska reaktioner är en nyckelkomponent i systemkemi, där reaktionsnätverk ger upphov till komplexa, emergenta beteenden. Denna avhandling syftar till att utnyttja en speciell egenskap hos dynamiska reaktionssystem - responsivitet.Det första kapitlet i denna avhandling introducerar dynamisk kovalent kemi och en allmän metod för att skapa enkla reaktionsnätverk genom att sammankoppla olika dynamiska kovalenta reaktioner. Begrepp inom systemkemi introduceras i termer av nätverkstopologi, responsivitet och reaktionssystem långt ifrån jämvikt, samtidigt som paralleller dras till naturliga system.Det andra kapitlet undersöker potentialen för nitroaldolreaktioner för dynamiska system. Nitroaldol-reaktioner används här för dynamisk polymerisation såväl som formaldehyd-responsiv nedbrytning av dynamiska polymerer. Simultan bildning och nedbrytning av polymer skapar ett emergent icke-jämviktsbeteende. Vidare används nitroaldol-producerade dioler i boronatesterbildning. Denna reaktivitet skapar en sammankoppling av två reaktioner som därmed influerar varandra. Genom att kombinera nitroaldol- och boronat-system öppnas möjligheterna att skapa boronatdynamerer av olika topologi.Det tredje kapitlet utforskar metallkoordinationseffekter i dynamiska reaktionsnätverk. Den nya basfria nitroaldolreaktionen beskriven i kapitel två utnyttjas här i ett reaktionsnätverk med hemiacetaler. Ett systemiskt svar på addition av metaller uppkommer således genom hemiacetal-metall-koordination. Under andra hälften av kapitlet demonstreras ett naturinspirerat dynamiskt iminkomplex som ger emergenta π-π-interaktioner som liknar en så kallad ”klaff-bro”. Variation av metallernas laddning samt den effektiva elektrostatiska karaktären hos substitutuenterna och liganderna ger kontroll över systemet och dess emergenta π-π-interaktioner.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2020. , p. 89
Series
TRITA-CBH-FOU ; 2020:9
Keywords [en]
stimuli-responsiveness, dynamic covalent reactions, systems chemistry, constitutional dynamics, non-equilibrium systems, nitroaldol reaction, dynamers, reversible polymerization, boronate ester, imine ligand, metal coordination, self–assembly, emergent properties, network topology.
Keywords [sv]
stimuli-responsivitet, dynamiska kovalenta reaktioner, systemkemi, konstitutionell dynamik, icke-jämviktssystem, nitroaldolreaktion, dynamerer, reversibel polymerisation, boronester, iminligand, metallkoordination, själv-organisation, emergenta egenskaper, nätverkstopologi.
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-267005ISBN: 978-91-7873-435-1 (print)ISBN: 978-91-7873-435-1 (electronic)OAI: oai:DiVA.org:kth-267005DiVA, id: diva2:1389425
Public defence
2020-02-21, F3, Lindstedtsvägen 26, Stockholm, 14:00 (English)
Opponent
Supervisors
Note

QC 20200203

Available from: 2020-02-03 Created: 2020-01-29 Last updated: 2020-02-03Bibliographically approved
List of papers
1. Formation and Out‐of‐Equilibrium, High/Low State Switching of a Nitroaldol Dynamer in Neutral Aqueous Media
Open this publication in new window or tab >>Formation and Out‐of‐Equilibrium, High/Low State Switching of a Nitroaldol Dynamer in Neutral Aqueous Media
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2020 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 59Article in journal (Refereed) In press
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-267001 (URN)10.1002/anie.201911706 (DOI)000508501500001 ()
Note

QC 20200203

Available from: 2020-01-29 Created: 2020-01-29 Last updated: 2020-02-03Bibliographically approved
2. Control Over Emergent π-π-Interactions in Double-Dynamic Coordination Complexes Through a Nature-Inspired Coordination-Triggered System
Open this publication in new window or tab >>Control Over Emergent π-π-Interactions in Double-Dynamic Coordination Complexes Through a Nature-Inspired Coordination-Triggered System
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

A complex self-assembly system based on coordination of dynamic imine/hemiacetal ligands isdemonstrated. Natural dipicolinic acid complexes are considered intercalants of certain bacterialDNA and implicated in thermal resistance of the dormant cell, and 6-formyl-2-picolinate was usedas building block. The dipicolinate-mimicking system showed an emergent and preferentialdynamic, drawbridge-style, π-π interaction effect to the opposing meridional ligand in octahedralcomplexes. The interactions proved to be influenced by the ligand net charge, the bridging arylgroup substitution, and the coordinating metal charge. The application scope of the effect isdiscussed.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-267003 (URN)
Note

QC 20200130

Available from: 2020-01-29 Created: 2020-01-29 Last updated: 2020-01-30Bibliographically approved
3. Rapidly Exchanging, Double-Dynamic, Catalyst-Free Nitroaldol-Hemiacetal Systems for Metal-Responsive Reversible Polymerization
Open this publication in new window or tab >>Rapidly Exchanging, Double-Dynamic, Catalyst-Free Nitroaldol-Hemiacetal Systems for Metal-Responsive Reversible Polymerization
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

A spontaneous, catalyst-free, reversible nitroaldol reaction is reported. The reaction wasused to create dynamic systems and to evaluate their scope and applicability. The thermodynamicand kinetic properties of the reaction were estimated, showing substantial solvent effects andatypical behavior regarding fluctuations and conversion overshoots. This was especially the casewhere the dynamic process was coupled with hemiacetal formation. Multifunctional building blockswere furthermore explored to generate responsive molecular systems, where zinc-coordinationcould be used to downregulate the nitroaldol reaction through the amplification of a dihemiacetalspecies. The systems were also extended to dynamic oligomer formation, where the molecularweight could be predictably upregulated by concentration increase and downregulated throughmetal coordination-induced amplification.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-267002 (URN)
Note

QC 20200130

Available from: 2020-01-29 Created: 2020-01-29 Last updated: 2020-01-30Bibliographically approved
4. Interdependent, Dynamic Nitroaldol and Stereoselective Boronic Ester Reactions for Complex Dynamers of Different Topologies
Open this publication in new window or tab >>Interdependent, Dynamic Nitroaldol and Stereoselective Boronic Ester Reactions for Complex Dynamers of Different Topologies
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Dynamic systems based on interdependent nitroaldol and boronic ester reactions have beendemonstrated. In aprotic solvents, nitroalkane-1,3-diols generated by the nitroaldol reaction weresusceptible to ester formation with different boronic acids, leading to significant stabilization of theadducts under basic conditions. Hydrolysis of the boronic esters occurred in the presence of water.The boronic ester formation was stereoselective as established using diastereomericnitroalkanediols. The use of bifunctional building blocks was furthermore established, allowing formain chain nitroaldol-boronate dynamers as well as complex dynamers with distinct topologies. Theshape and rigidity of the resulting dynamers showed apparent dependency on the configuration ofthe boronic acids.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-267004 (URN)
Note

QC 20200130

Available from: 2020-01-29 Created: 2020-01-29 Last updated: 2020-01-30Bibliographically approved

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