Iminoboronate Polymers as Dynamically Adaptable, Photoactive Materials

Lead Research Organisation: University of Cambridge
Department Name: Chemistry

Abstract

Polymers incorporating dynamic covalent bonds form a class of "smart" materials that are able to adapt to-or can be altered in response to-applied chemical or environmental stimuli. We propose a new class of dynamic, conjugated polymers based on the reversible iminoboronate ester bonding motif. Simple AB-type monomers incorporating aldehyde, amine, and boronic acid functionalities will polymerize together with diols to produce iminoboronate ester polymers. The presence of orthogonal dynamic imine and boronate ester bonds will allow us to develop easily functionalizable, and thus tuneable, multicomponent polymer materials that possess the ability to reorganise or adapt in response to various external stimuli. By incorporating electronically distinct diols, the photophysical properties of the conjugated polyimine polymer backbone may be tuned, providing a predictable pathway for attaining desired material properties. The unique set of characteristics of this materials system - highly tuneable electronic properties, structural rigidity through dative N-B stabilisation and electrochemical stability due to non-conjugated boron functionalization - promise to make these polymers strong candidates for light-emitting devices. (Additionally, obtaining a fundamental understanding of the affinity of the iminoboronate for electronically different diols will allow us to promote consecutive changes in polymer properties through successive diol exchanges.) These materials will be investigated as fluorescent polyreceptors for specific diols and as controllably crosslinkable or decrosslinkable materials with the addition or displacement of tetrols. Development of these high-value smart materials will lay the groundwork for the next generation of multifunctional devices, such as blue-light-emitting polymers with superior efficiency and electrochemical stability to the state-of-the-art poly(fluorene) OLEDs.

Planned Impact

Beyond the academic community, the development of new polymer materials and devices in this project will have impact on industry and the general public.

Industry: A key goal of this project is the production of new polymeric luminescent materials that are capable of emitting efficiently at a tuneable wavelength. In particular, the impact of a new family of materials for blue LEDs is very considerable, in the near term for use in full colour displays in phones, tablets and TVs, and in the longer term for OLED lighting. This is directly relevant to the very strong materials chemistry industrial activities in the UK, including CDT-Sumitomo in Cambridge and Merck in Southampton. These companies have developed state-of-the-art materials sets that are now used by Asian display manufacturers. For example, the 4k-resolution 55-inch OLED TV demonstrated by Panasonic is fabricated by printing of materials sets developed by CDT-Sumitomo. This falls very directly within the scope of 'Advanced Materials', one of the UK's 'Eight Great Technologies'.
Intellectual property (IP) will be protected and exploited in accordance with the published policy of the University of Cambridge to the benefit of all individuals and institutions involved. After the protection of any relevant IP, dissemination will be through publication in top international journals and domestic and international presentations. We will make sure that relevant IP is patented, potential licensees are recognised, and that possibilities for launching spin-outs are also properly identified.

General public: Appreciation and public support for scientific progress have underpinned technological progress in the UK ever since the practice of science became professionalised in the 19th century. We are committed to maintaining our side of this dialogue through explaining to the public what we do and why. One mechanism for this is press coverage of our research programme. The Nitschke group's 2009 Science paper generated a dozen stories in newspapers, TV, and radio across more than five countries, all with a positive bent. Another mechanism is structured outreach events; JRN will present his group's research to the 2014 international 'Pint of Science' festival (http://www.pintofscience.com/).

Education: In the context of undergraduate education, one of the Nitschke group's self-assembled systems will be highlighted in the next edition of a first-year undergraduate chemistry textbook and has already been adapted for use in undergraduate practical exercises.
 
Description New conjugated polymers have been prepared - several high-impact papers have been published, with more on the way. These polymers emit white light, and applications as conductive materials ('molecular wires') are being explored. We have also succeeded in controlling the left/right-handed helical twist of these polymers, which can control how these polymers may emit circularly polarized light. Such emission is relevant in the coming generation of new display applications (OLEDs).
Exploitation Route New conductive materials
New sensors
New light-emitting materials
Sectors Aerospace

Defence and Marine

Chemicals

Construction

Creative Economy

Digital/Communication/Information Technologies (including Software)

Electronics

Energy

Environment

Healthcare

Manufacturing

including Industrial Biotechology

Pharmaceuticals and Medical Biotechnology

Security and Diplomacy

URL http://www-jrn.ch.cam.ac.uk
 
Description Jake Greenfield, one of the project's principals, was selected to present his work on this project at the STEM for Britain event in Parliament (http://www.setforbritain.org.uk/2017event.asp) on 13 March 2017. This competitive selection provided a greater depth of understanding of the fundamental problems addressed in this project to our nation's decision-makers.
First Year Of Impact 2017
Sector Government, Democracy and Justice
Impact Types Societal

 
Title CCDC 1519037: Experimental Crystal Structure Determination 
Description Related Article: Jake L. Greenfield, Felix J. Rizzuto, Ieva Goldberga, Jonathan R. Nitschke|2017|Angew.Chem.,Int.Ed.|56|7541|doi:10.1002/anie.201702320 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mzp6h&sid=DataCite
 
Title CCDC 1541836: Experimental Crystal Structure Determination 
Description Related Article: Tanya K. Ronson, Wenjing Meng, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|9698|doi:10.1021/jacs.7b05202 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nrdng&sid=DataCite
 
Title CCDC 1541837: Experimental Crystal Structure Determination 
Description Related Article: Tanya K. Ronson, Wenjing Meng, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|9698|doi:10.1021/jacs.7b05202 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nrdph&sid=DataCite
 
Title CCDC 1541838: Experimental Crystal Structure Determination 
Description Related Article: Tanya K. Ronson, Wenjing Meng, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|9698|doi:10.1021/jacs.7b05202 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nrdqj&sid=DataCite
 
Title CCDC 1541839: Experimental Crystal Structure Determination 
Description Related Article: Tanya K. Ronson, Wenjing Meng, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|9698|doi:10.1021/jacs.7b05202 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nrdrk&sid=DataCite
 
Title CCDC 1541840: Experimental Crystal Structure Determination 
Description Related Article: Tanya K. Ronson, Wenjing Meng, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|9698|doi:10.1021/jacs.7b05202 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nrdsl&sid=DataCite
 
Title CCDC 1541841: Experimental Crystal Structure Determination 
Description Related Article: Tanya K. Ronson, Wenjing Meng, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|9698|doi:10.1021/jacs.7b05202 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nrdtm&sid=DataCite
 
Title CCDC 1541842: Experimental Crystal Structure Determination 
Description Related Article: Tanya K. Ronson, Wenjing Meng, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|9698|doi:10.1021/jacs.7b05202 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nrdvn&sid=DataCite
 
Title CCDC 1549079: Experimental Crystal Structure Determination 
Description Related Article: Felix J. Rizzuto, Daniel M. Wood, Tanya K. Ronson, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|11008|doi:10.1021/jacs.7b05788 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nzy9w&sid=DataCite
 
Title CCDC 1549080: Experimental Crystal Structure Determination 
Description Related Article: Felix J. Rizzuto, Daniel M. Wood, Tanya K. Ronson, Jonathan R. Nitschke|2017|J.Am.Chem.Soc.|139|11008|doi:10.1021/jacs.7b05788 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nzybx&sid=DataCite
 
Title CCDC 1577717: Experimental Crystal Structure Determination 
Description Related Article: Derrick A. Roberts, Ben S. Pilgrim, Giedre Sirvinskaite, Tanya K Ronson, Jonathan R. Nitschke|2018|J.Am.Chem.Soc.|140|9616|doi:10.1021/jacs.8b05082 
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.cc1pyr3h&sid=DataCite
 
Title CCDC 1577718: Experimental Crystal Structure Determination 
Description Related Article: Derrick A. Roberts, Ben S. Pilgrim, Giedre Sirvinskaite, Tanya K Ronson, Jonathan R. Nitschke|2018|J.Am.Chem.Soc.|140|9616|doi:10.1021/jacs.8b05082 
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.cc1pyr4j&sid=DataCite
 
Title CCDC 1577719: Experimental Crystal Structure Determination 
Description Related Article: Derrick A. Roberts, Ben S. Pilgrim, Giedre Sirvinskaite, Tanya K Ronson, Jonathan R. Nitschke|2018|J.Am.Chem.Soc.|140|9616|doi:10.1021/jacs.8b05082 
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.cc1pyr5k&sid=DataCite
 
Title CCDC 1844532: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd1b&sid=DataCite
 
Title CCDC 1844533: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd2c&sid=DataCite
 
Title CCDC 1844534: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd3d&sid=DataCite
 
Title CCDC 1844535: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd4f&sid=DataCite
 
Title CCDC 1844536: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd5g&sid=DataCite
 
Title CCDC 1844537: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd6h&sid=DataCite
 
Title CCDC 1844538: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd7j&sid=DataCite
 
Title CCDC 1844539: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd8k&sid=DataCite
 
Title CCDC 1844540: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxd9l&sid=DataCite
 
Title CCDC 1844541: Experimental Crystal Structure Determination 
Description Related Article: Evan N. Keyzer, Alexandru Sava, Tanya K. Ronson, Jonathan R. Nitschke, Anna J. McConnell|2018|Chem.-Eur.J.|24|12000|doi:10.1002/chem.201802790 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zxdbm&sid=DataCite
 
Title Data supporting "A Molecular Movie of Ultrafast Singlet Fission " 
Description This data set contains all data underlying the figures in the main text and supporting information. The information on how the data was acquired and processed is detailed in the open access manuscript + SI which has been deposited in this repository ("A Molecular Movie of Singlet Fission") and is also available open-access via the publisher Nature Communications under the same title. Main Figures: Figure 1 - Transient absorption data on DP-Mes and transient cuts Figure 2 - Fourier transform power map of the data in Figure 1 as well as complementary Raman spectra for comparison Figure 3 - Comparison of directly generated and 'transferred' vibrational coherence spectrum Figure 4 - Theoretical modelling of the collective vibrational coherences separated according to symmetry groups. The data was converted into a quasi-resonance Raman spectrum and compared to the data in Figure 3. Figure 5 - Extracted structural parameters (bond length and dihedral angle) as function of time as well as the correlation of the displacement coherences for tuning and coupling modes are shown. SI Figures: Figure S6 - contains the Fourier amplitude spectrum of the tuning modes retrieved from theory (not resonance Raman) Figure S7 - provides the maximum displacement amplitudes as a function of frequency for the B1 coupling modes Figure S8 - displays the S1 decay dynamics from theory as a function of modifying the coupling modes as well as the extraced exponential decay dynamics. Figure S9 - contains the transient absorption spectrum of DP-Mes (a) compared to TIPS-pentacene (b) as well as a comparison of the direct and transferred coherence properties of DP-Mes (c) and TIPS-pentacene (d). The transferred spectrum of TIPS is compared to the transferred and direct spectrum of DP-Mes in e Figure S10 - Full time evolution from theory of the S1 and 1TT population dynamics (a), central dimer bond length (b) and dihedral angle (c) Figure S11 - Temperature Dependence of transient absorption measurements in DP-Mes at 295 K (a) and 5 K (b). The dynamics for S1 (c) and 1TT (d) as a function of temperature are also give.n Video: The video is a smoothed representation of the time-dependent structure extracted from theory. all structures are saved after each other in the conventional xyz file format. These are best opened with a molecular editor such as Avogadro or VMD. 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
URL https://www.repository.cam.ac.uk/handle/1810/296198
 
Title Research Data Supporting: 'Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors' 
Description Zip folder containing the data that forms the figures in the main text of the publication. The Microsoft Excel file contains the transient absorption spectra and related kinetics for the neat BF2 and dilution series in CBP films, presented in wavelength (nm) and time (picoseconds), respectively. Also included in the Excel file are the photoluminescence-detected magnetic resonance spectra for the neat BF2 film, taken at different applied microwave magnetic field strengths (B1). The photoluminescence-detected magnetic resonance spectra are presented in magnetic field strength, B0 (mT). See the main manuscript for more details. 
Type Of Material Database/Collection of data 
Year Produced 2021 
Provided To Others? Yes  
URL https://www.repository.cam.ac.uk/handle/1810/330185
 
Title Research data supporting "Vibrationally Assisted Intersystem Crossing in Benchmark Thermally Activated Delayed Fluorescence Molecules" 
Description Raw data for manuscript titled 'Vibrationally-assisted intersystem crossing in benchmark thermally activated delayed fluorescence molecules.' Data includes absorption and photoluminescence spectra for 2CzPN and 4CzIPN (Fig1b_Abs_2CzPN, Fig1b_Abs_4CzIPN, Fig1b_PL_2CzPN, Fig1b_PL_4CzIPN); transient electron spin resonance spectra for 2CzPN and 4CzIPN (Fig2c_2CzPN_0p4us, Fig2d_4CzIPN_0p4us); probability distributions for zero-field splitting in 2CzPN and 4CzIPN (Fig3a_2CzPN_ZFS_probability_distribution, Fig3b_4CzIPN_ZFS_probability_distribution); plots of zero-field splitting as a function of overlap index in 2CzPN and 4CzIPN (Fig3c_2CzPN_ZFS_overlap_idx, Fig3d_4CzIPN_ZFS_overlap_idx); and density plots (field versus time) of transient electron spin resonance spectra of 2CzPN and 4CzIPN (FigS1_TrESR_2CzPN_420nm_exc, FigS1_TrESR_4CzIPN_460nm_exc). 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title Research data supporting: Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters 
Description A Microsoft Excel file containing the data that forms the figures in the main text of the publication. The Microsoft Excel file contains the ultrafast transient absorption and photoluminescence data for TXO-TPA and 4CzIPN, presented in wavelength (nm) and time (ps). Also included is the steady state Raman and impulsive vibrational spectra of TXO-TPA and 4CzIPN at 0.5, 3, and 10 ps (in wavenumbers). The full datasets for the quantum-chemical molecular dynamics simulations of TXO-TPA are also presented. See the main manuscript for more details. 
Type Of Material Database/Collection of data 
Year Produced 2022 
Provided To Others? Yes  
URL https://www.repository.cam.ac.uk/handle/1810/339315