scholarly journals Designing Singlet Fission Candidates from Donor-Acceptor Copolymers

2020 ◽  
Author(s):  
Jacob Terence Blaskovits ◽  
Maria Fumanal ◽  
Sergi Vela ◽  
Clemence Corminboeuf
Keyword(s):  
High Throughput Screening ◽  
Molecular Design ◽  
Crystal Packing ◽  
Cost Effective ◽  
Frontier Molecular Orbital ◽  
Structure Property ◽  
Singlet Fission ◽  
Structure Property Relationships ◽  
Large Databases ◽  
Donor Acceptor

<p>Singlet Fission (SF) has demonstrated significant promise for boosting the power conversion efficiency (PCE) of solar cells. Traditionally, SF is targeted as an intermolecular process, however its dependence on crystal packing makes molecular design difficult. In contrast, intramolecular SF (iSF) enables the exploration of tunable bi-chromophoric systems following well-defined structure-property relationships. In this work, we propose a set of parameters to screen conjugated donor-acceptor copolymer candidates with potential iSF behaviour. We focus our analysis on the E(S<sub>1</sub>)>2E(T<sub>1</sub>) thermodynamic condition and on the appropriate charge transfer (CT) character of S<sub>1</sub>. We map the CT character with respect to the frontier molecular orbital (FMO) energies of the constituent monomers, providing a cost-effective protocol for an accelerated screening of promising iSF donor-acceptor pairs, while minimizing the number of computations. These parameters are applied to a chemically diverse, curated library of 81 truncated dimers of synthetically feasible donor-acceptor copolymers. From our dataset, four candidates are flagged for iSF, two of which were previously experimentally reported. This protocol is envisioned to be scaled up for the high-throughput screening of large databases of donor-acceptor dimers for the design and identification of conjugated polymers capable of iSF. </p>

scholarly journals Designing Singlet Fission Candidates from Donor-Acceptor Copolymers

2020 ◽  
Author(s):  
Jacob Terence Blaskovits ◽  
Maria Fumanal ◽  
Sergi Vela ◽  
Clemence Corminboeuf
Keyword(s):  
High Throughput Screening ◽  
Molecular Design ◽  
Crystal Packing ◽  
Cost Effective ◽  
Frontier Molecular Orbital ◽  
Structure Property ◽  
Singlet Fission ◽  
Structure Property Relationships ◽  
Large Databases ◽  
Donor Acceptor

<p>Singlet Fission (SF) has demonstrated significant promise for boosting the power conversion efficiency (PCE) of solar cells. Traditionally, SF is targeted as an intermolecular process, however its dependence on crystal packing makes molecular design difficult. In contrast, intramolecular SF (iSF) enables the exploration of tunable bi-chromophoric systems following well-defined structure-property relationships. In this work, we propose a set of parameters to screen conjugated donor-acceptor copolymer candidates with potential iSF behaviour. We focus our analysis on the E(S<sub>1</sub>)>2E(T<sub>1</sub>) thermodynamic condition and on the appropriate charge transfer (CT) character of S<sub>1</sub>. We map the CT character with respect to the frontier molecular orbital (FMO) energies of the constituent monomers, providing a cost-effective protocol for an accelerated screening of promising iSF donor-acceptor pairs, while minimizing the number of computations. These parameters are applied to a chemically diverse, curated library of 81 truncated dimers of synthetically feasible donor-acceptor copolymers. From our dataset, four candidates are flagged for iSF, two of which were previously experimentally reported. This protocol is envisioned to be scaled up for the high-throughput screening of large databases of donor-acceptor dimers for the design and identification of conjugated polymers capable of iSF. </p>

scholarly journals Designing Singlet Fission Candidates from Donor-Acceptor Copolymers

2020 ◽  
Author(s):  
Jacob Terence Blaskovits ◽  
Maria Fumanal ◽  
Sergi Vela ◽  
Clemence Corminboeuf
Keyword(s):  
High Throughput Screening ◽  
Molecular Design ◽  
Crystal Packing ◽  
Cost Effective ◽  
Frontier Molecular Orbital ◽  
Structure Property ◽  
Singlet Fission ◽  
Structure Property Relationships ◽  
Large Databases ◽  
Donor Acceptor

<p>Singlet Fission (SF) has demonstrated significant promise for boosting the power conversion efficiency (PCE) of solar cells. Traditionally, SF is targeted as an intermolecular process, however its dependence on crystal packing makes molecular design difficult. In contrast, intramolecular SF (iSF) enables the exploration of tunable bi-chromophoric systems following well-defined structure-property relationships. In this work, we propose a set of parameters to screen conjugated donor-acceptor copolymer candidates with potential iSF behaviour. We focus our analysis on the E(S<sub>1</sub>)>2E(T<sub>1</sub>) thermodynamic condition and on the appropriate charge transfer (CT) character of S<sub>1</sub>. We map the CT character with respect to the frontier molecular orbital (FMO) energies of the constituent monomers, providing a cost-effective protocol for an accelerated screening of promising iSF donor-acceptor pairs, while minimizing the number of computations. These parameters are applied to a chemically diverse, curated library of 81 truncated dimers of synthetically feasible donor-acceptor copolymers. From our dataset, four candidates are flagged for iSF, two of which were previously experimentally reported. This protocol is envisioned to be scaled up for the high-throughput screening of large databases of donor-acceptor dimers for the design and identification of conjugated polymers capable of iSF. </p>

scholarly journals Identifying the Trade-off between Intramolecular Singlet Fission Requirements in Donor-Acceptor Copolymers

2020 ◽  
Author(s):  
Jacob Terence Blaskovits ◽  
Maria Fumanal ◽  
Sergi Vela ◽  
Raimon Fabregat ◽  
Clemence Corminboeuf
Keyword(s):  
Single Molecule ◽  
Molecular Design ◽  
Relative Energy ◽  
Frontier Molecular Orbital ◽  
Great Promise ◽  
Singlet Fission ◽  
Trade Off ◽  
Singlet Exciton ◽  
Donor Acceptor ◽  
Photoinduced Charge

Intramolecular singlet fission (iSF) has shown potential to improve the power conversion efficiency in photovoltaic devices by promoting the splitting of a photon-absorbing singlet exciton into two triplet excitons within a single molecule. Among different possibilities, the donor-acceptor modular strategy of copolymers has shown great promise in its ability to undergo iSF under certain conditions. However, the number of iSF donor-acceptor copolymers reported in the literature remains remarkably narrow and clear trends for the molecular design of better candidates have not yet been established. In this work, we identify the trade-off between the main iSF requirements of the donor-acceptor strategy and formulate design rules that allow them to be tuned simultaneously in a fragment-based approach. Based on a library of 2944 donor-acceptor copolymers, we establish simple guidelines to build promising novel materials for iSF. These consist in (1st) selecting an acceptor core with high intrinsic singlet-triplet splitting, (2nd) locating a donor with a larger monomer frontier molecular orbital (FMO) gap than that of the acceptor, and (3rd) tuning the relative energy of donor and/or acceptor FMOs through functionalization to promote photoinduced charge transfer in the resulting polymer. Remarkably, systems containing benzothiadiazole and thiophehe-1,1-dioxide acceptors, which have been shown to undergo iSF, fulfill all criteria simultaneously when paired with appropriate donors. This is due to their particular electronic features, which make them highly promising candidates in the quest for iSF materials.<br>

scholarly journals Identifying the Trade-off between Intramolecular Singlet Fission Requirements in Donor-Acceptor Copolymers

2020 ◽  
Author(s):  
Jacob Terence Blaskovits ◽  
Maria Fumanal ◽  
Sergi Vela ◽  
Raimon Fabregat ◽  
Clemence Corminboeuf
Keyword(s):  
Single Molecule ◽  
Molecular Design ◽  
Relative Energy ◽  
Frontier Molecular Orbital ◽  
Great Promise ◽  
Singlet Fission ◽  
Trade Off ◽  
Singlet Exciton ◽  
Donor Acceptor ◽  
Photoinduced Charge

Intramolecular singlet fission (iSF) has shown potential to improve the power conversion efficiency in photovoltaic devices by promoting the splitting of a photon-absorbing singlet exciton into two triplet excitons within a single molecule. Among different possibilities, the donor-acceptor modular strategy of copolymers has shown great promise in its ability to undergo iSF under certain conditions. However, the number of iSF donor-acceptor copolymers reported in the literature remains remarkably narrow and clear trends for the molecular design of better candidates have not yet been established. In this work, we identify the trade-off between the main iSF requirements of the donor-acceptor strategy and formulate design rules that allow them to be tuned simultaneously in a fragment-based approach. Based on a library of 2944 donor-acceptor copolymers, we establish simple guidelines to build promising novel materials for iSF. These consist in (1st) selecting an acceptor core with high intrinsic singlet-triplet splitting, (2nd) locating a donor with a larger monomer frontier molecular orbital (FMO) gap than that of the acceptor, and (3rd) tuning the relative energy of donor and/or acceptor FMOs through functionalization to promote photoinduced charge transfer in the resulting polymer. Remarkably, systems containing benzothiadiazole and thiophehe-1,1-dioxide acceptors, which have been shown to undergo iSF, fulfill all criteria simultaneously when paired with appropriate donors. This is due to their particular electronic features, which make them highly promising candidates in the quest for iSF materials.<br>

Structure−Property Relationships of Donor/Acceptor-Functionalized Tetrakis(phenylethynyl)benzenes and Bis(dehydrobenzoannuleno)benzenes

2005 ◽  
Vol 127 (8) ◽  
pp. 2464-2476 ◽  
Author(s):  
Jeremiah A. Marsden ◽  
Jeremie J. Miller ◽  
Laura D. Shirtcliff ◽  
Michael M. Haley
Keyword(s):  
Structure Property ◽  
Structure Property Relationships ◽  
Donor Acceptor

scholarly journals Molecular design strategy for practical singlet fission materials: The charm of donor/acceptor decorated quinoidal structure

CCS Chemistry ◽  
2021 ◽  
pp. 1-17
Author(s):  
Long Wang ◽  
Xiaomei Shi ◽  
Shishi Feng ◽  
WanZhen Liang ◽  
Hongbing Fu ◽  
...  
Keyword(s):  
Molecular Design ◽  
Design Strategy ◽  
Singlet Fission ◽  
Donor Acceptor

Donor-Acceptor-Functionalized Tetraethynylethenes with Nitrothienyl Substituents: Structure-Property Relationships

2000 ◽  
Vol 83 (7) ◽  
pp. 1484-1508 ◽  
Author(s):  
Rik R. Tykwinski ◽  
Anouk Hilger ◽  
François Diederich ◽  
Hans Peter Lüthi ◽  
Paul Seiler ◽  
...  
Keyword(s):  
Structure Property ◽  
Structure Property Relationships ◽  
Donor Acceptor

scholarly journals Crystal chemistry and photomechanical behavior of 3,4-dimethoxycinnamic acid: correlation between maximum yield in the solid-state topochemical reaction and cooperative molecular motion

IUCrJ ◽  
2015 ◽  
Vol 2 (6) ◽  
pp. 653-660 ◽  
Author(s):  
Manish Kumar Mishra ◽  
Arijit Mukherjee ◽  
Upadrasta Ramamurty ◽  
Gautam R. Desiraju
Keyword(s):  
Solid State ◽  
Crystal Packing ◽  
Maximum Yield ◽  
Structure Property ◽  
Crystal Forms ◽  
Individual Crystal ◽  
Structure Property Relationships ◽  
Molecular Movement ◽  
Truxillic Acid ◽  
The Individual

A new monoclinic polymorph, form II (P21/c,Z= 4), has been isolated for 3,4-dimethoxycinnamic acid (DMCA). Its solid-state 2 + 2 photoreaction to the corresponding α-truxillic acid is different from that of the first polymorph, the triclinic form I (P\bar 1,Z= 4) that was reported in 1984. The crystal structures of the two forms are rather different. The two polymorphs also exhibit different photomechanical properties. Form I exhibits photosalient behavior but this effect is absent in form II. These properties can be explained on the basis of the crystal packing in the two forms. The nanoindentation technique is used to shed further insights into these structure−property relationships. A faster photoreaction in form I and a higher yield in form II are rationalized on the basis of the mechanical properties of the individual crystal forms. It is suggested that both Schmidt-type and Kaupp-type topochemistry are applicable for the solid-statetrans-cinnamic acid photodimerization reaction. Form I of DMCA is more plastic and seems to react under Kaupp-type conditions with maximum molecular movements. Form II is more brittle, and its interlocked structure seems to favor Schmidt-type topochemistry with minimum molecular movement.

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