Triplet Formation in a 9,10-Bis(phenylethynyl)anthracene Dimer and Trimer Occurs by Charge Recombination Rather than Singlet Fission

We present an experimental study investigating the solvent-dependent dynamics of a 9,10-bis(phenylethynyl)anthracene monomer, dimer, and trimer. Using transient absorption spectroscopy, we have discovered that triplet excited state formation in the dimer and trimer molecules in polar solvents is a consequence of charge recombination subsequent to symmetry-breaking charge separation rather than singlet fission. Total internal reflection emission measurements of the monomer demonstrate that excimer formation serves as the primary decay pathway at a high concentration. In the case of highly concentrated solutions of the trimer, we observe evidence of triplet formation without the prior formation of a charge-separated state. We postulate that this is attributed to the formation of small aggregates, suggesting that oligomers mimicking the larger chromophore counts in crystals could potentially facilitate singlet fission. Our experimental study sheds light on the intricate dynamics of the 9,10-bis(phenylethynyl)anthracene system, elucidating the role of solvent- and concentration-dependent factors for triplet formation and charge separation

Molecular rotational conformation controls the rate of singlet fission and triplet decay in pentacene dimers

Three pentacene dimers have been synthesized to investigate the effect of molecular rotation and rotational conformations on singlet fission (SF). In all three dimers, the pentacene units are linked by a 1,4-diethynylphenylene spacer that provides almost unimpeded rotational freedom between the pentacene- and phenylene-subunits in the parent dimer. Substituents on the phenylene spacer add varying degrees of steric hindrance that restricts both the rotation and the equilibrium distribution of different conformers; the less restricted conformers exhibit faster SF and more rapid subsequent triplet-pair recombination. Furthermore, the rotational conformers have small shifts in their absorption spectra and this feature has been used to selectively excite different conformers and study the resulting SF. Femtosecond transient absorption studies at 100 K reveal that the same dimer can have orders of magnitude faster SF in a strongly coupled conformer compared to a more weakly coupled one. Measurements in polystyrene further show that the SF rate is nearly independent of viscosity whereas the triplet pair lifetime is considerably longer in a high viscosity medium. The results provide insight into design criteria for maintaining high initial SF rate while suppressing triplet recombination in intramolecular singlet fission

Nonlinear Optical Properties of Polyynes: An Experimental Prediction for Carbyne

We present the experimental determination of the vibrational contribution to molecular second hyperpolarizability (Îvib) of very long polyynes that have been recently made available thanks to progress in chemical synthesis. Based on a simple theoretical model, the available experimental data allow estimating the asymptotic behavior of the vibrational contribution to molecular hyperpolarizability for increasing chain length

Förster Resonance Energy Transfer Sensitized Singlet Fission in BODIPY-Pentacene Dimer Conjugates

In the present work, the energy donor 4,4-difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY) is used for the first time in combination with a pentacene dimer (Pnc2) to provide the conjugate BODIPYPnc2 that features absorption throughout a large part of the solar spectrum. Upon photoexcitation, the singlet excited state energy of BODIPY is transferred to the pentacene dimer via intramolecular Förster resonance energy transfer (FRET). Subsequently, the pentacene dimer undergoes intramolecular singlet fission. In this process, a singlet correlated triplet pair is generated from the first singlet excited state via coupling to an intermediate state. The results show that solvent polarity has an influence on the system, with the largest FRET rate (i.e., 7.46 × 1011 s−1) being obtained in the most polar solvent (namely, benzonitrile) along with the largest triplet quantum yield (i.e., 207 ± 20%)A.-S.W., G.L., and I.P. contributed equally to this work. D.M.G. thanks the financial support from ″the German Research Foundation (DFG) via SFB 953 “Synthetic Carbon Allotropes” and “Solar Technologies go Hybrid (SolTech)” Initiative of the Bavarian Ministry for Science. T.T. acknowledges financial support from MICINN (PID2020-116490GB-I00 and TED2021-131255B-C43), the Comunidad de Madrid and the Spanish State through the Recovery, Transformation and Resilience Plan [“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados], and the European Union through the Next Generation EU funds. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). R.R.T. acknowledges funding from the Natural Sciences and Engineering Research Council of Canada (NSERC, grant no. RGPIN-2017-05052) and the Canada Foundation for Innovation (CFI

Stable and Solution-Processable Cumulenic sp-Carbon Wires: A New Paradigm for Organic Electronics

[EN] Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp(2)-hybridized carbon molecules, either in the form of pi-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to molecular devices. The recent observation of the field-effect in microcrystalline cumulenes suggests their potential applications in solution-processed thin-film transistors but concerns surrounding the stability and electronic performance have precluded developments in this direction. In the present study, ideal field-effect characteristics are demonstrated for solution-processed thin films of tetraphenyl[3]cumulene, the shortest semiconducting CAW. Films are deposited through a scalable, large-area, meniscus-coating technique, providing transistors with hole mobilities in excess of 0.1 cm(2 )V(-1 )s(-1), as well as promising operational stability under dark conditions. These results offer a solid foundation for the exploitation of a vast class of molecular semiconductors for organic electronics based on sp-hybridized carbon systems and create a previously unexplored paradigm.E.G.F. acknowledges the support through the EU Horizon 2020 research and innovation program, H2020-FETOPEN-01-2018-2020 (FET-Open Challenging Current Thinking), "LION-HEARTED", grant agreement no. 828984. C.S.C. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program ERC-Consolidator Grant (ERC CoG 2016 EspLORE grant agreement no. 724610, website: ). R.R.T. acknowledges funding from the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Canada Foundation for Innovation (CFI). This work was partially supported by the European Union's H2020-EU.4.b. - Twinning of research institutions "GREENELIT", grant agreement number 951747. GIWAXS experiments were performed at BL11 NCD-SWEET beamline at ALBA Synchrotron (Spain) with the collaboration of ALBA staff. This work was in part carried out at Polifab, the micro- and nanotechnology centre of the Politecnico di Milano. Open access funding provided by Istituto Italiano di Tecnologia within the CRUI-CARE Agreement