Two dimensional supramolecular networks on insulators: structural organisation, fluorescence and host-guest interactions
Lead Research Organisation:
University of Nottingham
Department Name: Sch of Chemistry
Abstract
This project focuses on the ability to control the organisation of molecules on the molecular level, to specifically determine their precise positioning and to understand the effect of their relative positions on their fluorescence. The study builds upon our recent discovery that it is possible to structurally characterise molecular arrays on insulating surfaces under atmospheric conditions with a high degree of precision by atomic force microscopy (AFM), moving beyond previous studies that used conducting surfaces. As a result we are now able to probe molecular properties, such as fluorescence, which were previously quenched by the supporting, conducting surface.
We now seek to understand to what degree these properties can be controlled and how entrapment of guest molecules within our arrays, which are porous, affects that fluorescence. We will develop a detailed understanding of the effect of guest trapping by the surface-based arrays and demonstrate that through change in the fluorescence signal we can specifically recognise trapped guest molecules working towards molecular-scale sensing systems.
We now seek to understand to what degree these properties can be controlled and how entrapment of guest molecules within our arrays, which are porous, affects that fluorescence. We will develop a detailed understanding of the effect of guest trapping by the surface-based arrays and demonstrate that through change in the fluorescence signal we can specifically recognise trapped guest molecules working towards molecular-scale sensing systems.
Planned Impact
Our research directly addresses the topics of self-assembly of new materials, in particular extended arrays. Our work is very closely aligned with the objectives of the EPSRC Grand Challenges in Chemistry, Directed Assemblies of Extended Structures with Targeted Properties and Physics, Nanoscale Design of Functional Materials, which envisage an increasingly important role for self-assembly approaches in the manufacture of new functional materials.
The EPSRC have recognized that controlling functional and structural properties at a level of complexity comparable with that displayed by biological systems is an extremely long term goal, which may require in excess of 20 years. However they have also recognised that self-assembly of materials has the potential for far-reaching economic impact. The objectives of our project, particularly our focus on determining the influence of guest molecules on host-guest fluorescence and our exploration of the potential of fluorescent 2D supramolecular networks for molecular recognition, are likely to come toward fruition the end of the three year project and we will seek to develop and exploit the impact of our research through the organization of a multi-disciplinary one-day meeting for both academic and industrial parties interested in the development of this research field and the emergent properties from the technology that we seek to develop.
The team have a strong track record in communicating their science to wider audiences and in using the media to publicise their research. We believe that the proposed research is ideal for public communication and therefore we will bid to present our research at the Royal Society Exhibition in the latter years of the project. A major impact from the research will be the output of trained researchers, 2 postdocs and a PhD student, whose training will be enhanced through their participation in an interdisciplinary grouping. This cohort of researchers will provide a highly significant impact through the availability of research staff to support an expansion of research into self-assembly in the UK over the next decade. Any results of commercial significance that arise, possibly related to synthetic methodology or development of theoretical models will be protected through the Business Partnership Unit (BPU) within the School of Chemistry at Nottingham.
The EPSRC have recognized that controlling functional and structural properties at a level of complexity comparable with that displayed by biological systems is an extremely long term goal, which may require in excess of 20 years. However they have also recognised that self-assembly of materials has the potential for far-reaching economic impact. The objectives of our project, particularly our focus on determining the influence of guest molecules on host-guest fluorescence and our exploration of the potential of fluorescent 2D supramolecular networks for molecular recognition, are likely to come toward fruition the end of the three year project and we will seek to develop and exploit the impact of our research through the organization of a multi-disciplinary one-day meeting for both academic and industrial parties interested in the development of this research field and the emergent properties from the technology that we seek to develop.
The team have a strong track record in communicating their science to wider audiences and in using the media to publicise their research. We believe that the proposed research is ideal for public communication and therefore we will bid to present our research at the Royal Society Exhibition in the latter years of the project. A major impact from the research will be the output of trained researchers, 2 postdocs and a PhD student, whose training will be enhanced through their participation in an interdisciplinary grouping. This cohort of researchers will provide a highly significant impact through the availability of research staff to support an expansion of research into self-assembly in the UK over the next decade. Any results of commercial significance that arise, possibly related to synthetic methodology or development of theoretical models will be protected through the Business Partnership Unit (BPU) within the School of Chemistry at Nottingham.
Publications
Albar J
(2018)
Adsorption of Hexacontane on Hexagonal Boron Nitride
in The Journal of Physical Chemistry C
Alkhamisi M
(2018)
The growth and fluorescence of phthalocyanine monolayers, thin films and multilayers on hexagonal boron nitride.
in Chemical communications (Cambridge, England)
Almuhana A
(2021)
Retention of perylene diimide optical properties in solid-state materials through tethering to nanodiamonds
in Journal of Materials Chemistry C
Haddow S
(2018)
Perylene Diimide Triple Helix Formation in the Solid State
in Crystal Growth & Design
James T
(2023)
Electroluminescence from a phthalocyanine monolayer encapsulated in a van der Waals tunnel diode
in Molecular Physics
Judd CJ
(2020)
Structural characterisation of molecular conformation and the incorporation of adatoms in an on-surface Ullmann-type reaction.
in Communications chemistry
Kerfoot J
(2018)
Substrate-induced shifts and screening in the fluorescence spectra of supramolecular adsorbed organic monolayers.
in The Journal of chemical physics
Kerfoot J
(2019)
Two-Dimensional Diffusion of Excitons in a Perylene Diimide Monolayer Quenched by a Fullerene Heterojunction
in The Journal of Physical Chemistry C
Kerfoot J
(2020)
Fluorescence and Electroluminescence of J-Aggregated Polythiophene Monolayers on Hexagonal Boron Nitride.
in ACS nano
Korolkov VV
(2017)
Supramolecular heterostructures formed by sequential epitaxial deposition of two-dimensional hydrogen-bonded arrays.
in Nature chemistry
Korolkov VV
(2019)
Ultra-high resolution imaging of thin films and single strands of polythiophene using atomic force microscopy.
in Nature communications
Korolkov VV
(2017)
Supramolecular networks stabilise and functionalise black phosphorus.
in Nature communications
Kudrynskyi Z
(2020)
Resonant tunnelling into the two-dimensional subbands of InSe layers
in Communications Physics
Llewellyn BA
(2016)
Thionated perylene diimides with intense absorbance in the near-IR.
in Chemical communications (Cambridge, England)
Mali KS
(2017)
Frontiers of supramolecular chemistry at solid surfaces.
in Chemical Society reviews
Mangham B
(2020)
Influence of molecular design on radical spin multiplicity: characterisation of BODIPY dyad and triad radical anions.
in Physical chemistry chemical physics : PCCP
Martin HJ
(2018)
Influence of Hydrogen-Bonding Interactions on Nuclearity and Structure of Palladium Tiara-like Complexes.
in ACS omega
Mason SE
(2019)
AIRBED: A Simplified Density Functional Theory Model for Physisorption on Surfaces.
in Journal of chemical theory and computation
Pearce N
(2018)
Thionated naphthalene diimides: tuneable chromophores for applications in photoactive dyads.
in Physical chemistry chemical physics : PCCP
Pearce N
(2020)
Electrochemical and spectroelectrochemical investigations of perylene peri-tetracarbonyl species
in Dyes and Pigments
Pearce N
(2018)
Thionated Perylene Diimide-Phenothiazine Dyad: Synthesis, Structure, and Electrochemical Studies.
in ACS omega
Pfeiffer CR
(2017)
Complexity of two-dimensional self-assembled arrays at surfaces.
in Chemical communications (Cambridge, England)
Svatek SA
(2020)
Triplet Excitation and Electroluminescence from a Supramolecular Monolayer Embedded in a Boron Nitride Tunnel Barrier.
in Nano letters
Description | Significant Progress was made in delivering the objectives of this award. We have successfully made target molecules that are capable of supramolecular recognition processes and fluorescence and the project delivered enhanced understanding how substrate-surface interactions and surface-based self assembly affect the photophysical properties of the absorbed species, the main objective of the project. |
Exploitation Route | In the first instance our results will progress academic research in the area. |
Sectors | Chemicals |
Description | The research in this project underpinned the development of a book entitled "Supramolecular Chemistry on Surfaces. 2D Networks and 2D Structures" (Wiley-VCH, 2022) edited by PI Champness. |
First Year Of Impact | 2022 |
Sector | Chemicals |
Impact Types | Cultural |
Title | CCDC 1868841: Experimental Crystal Structure Determination |
Description | Related Article: Nicholas Pearce, E. Stephen Davies, William Lewis, and Neil R. Champness|2018|ACS Omega|3|14236|doi:10.1021/acsomega.8b02457 |
Type Of Material | Database/Collection of data |
Year Produced | 2018 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc20qp6n&sid=DataCite |
Title | CCDC 1868842: Experimental Crystal Structure Determination |
Description | Related Article: Nicholas Pearce, E. Stephen Davies, William Lewis, and Neil R. Champness|2018|ACS Omega|3|14236|doi:10.1021/acsomega.8b02457 |
Type Of Material | Database/Collection of data |
Year Produced | 2018 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc20qp7p&sid=DataCite |
Title | CCDC 1868843: Experimental Crystal Structure Determination |
Description | Related Article: Nicholas Pearce, E. Stephen Davies, William Lewis, and Neil R. Champness|2018|ACS Omega|3|14236|doi:10.1021/acsomega.8b02457 |
Type Of Material | Database/Collection of data |
Year Produced | 2018 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc20qp8q&sid=DataCite |
Title | CCDC 1868844: Experimental Crystal Structure Determination |
Description | Related Article: Nicholas Pearce, E. Stephen Davies, William Lewis, and Neil R. Champness|2018|ACS Omega|3|14236|doi:10.1021/acsomega.8b02457 |
Type Of Material | Database/Collection of data |
Year Produced | 2018 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc20qp9r&sid=DataCite |
Title | CCDC 1868845: Experimental Crystal Structure Determination |
Description | Related Article: Nicholas Pearce, E. Stephen Davies, William Lewis, and Neil R. Champness|2018|ACS Omega|3|14236|doi:10.1021/acsomega.8b02457 |
Type Of Material | Database/Collection of data |
Year Produced | 2018 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc20qpbs&sid=DataCite |
Title | CCDC 1935057: Experimental Crystal Structure Determination |
Description | Related Article: Barry Mangham, Magnus W. D. Hanson-Heine, E. Stephen Davies, Alisdair Wriglesworth, Michael W. George, William Lewis, Deborah L. Kays, Jonathan McMaster, Nicholas A. Besley, Neil R. Champness|2020|Phys.Chem.Chem.Phys.(PCCP)|22|4429|doi:10.1039/C9CP06427C |
Type Of Material | Database/Collection of data |
Year Produced | 2020 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22yl6v&sid=DataCite |
Title | CCDC 1935059: Experimental Crystal Structure Determination |
Description | Related Article: Barry Mangham, Magnus W. D. Hanson-Heine, E. Stephen Davies, Alisdair Wriglesworth, Michael W. George, William Lewis, Deborah L. Kays, Jonathan McMaster, Nicholas A. Besley, Neil R. Champness|2020|Phys.Chem.Chem.Phys.(PCCP)|22|4429|doi:10.1039/C9CP06427C |
Type Of Material | Database/Collection of data |
Year Produced | 2020 |
Provided To Others? | Yes |
URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc22yl8x&sid=DataCite |