Article
Chemistry, Multidisciplinary
Joseph K. Gallaher, Katherine M. Wright, Laszlo Frazer, Rowan W. MacQueen, Maxwell J. Crossley, Felix N. Castellano, Timothy W. Schmidt
Summary: The performance of a perylene monoimide annihilator in a photochemical upconversion composition shows promising results, outperforming the commonly used rubrene annihilator at low excitation intensity. However, its performance is hindered under strong excitation due to a low annihilation singlet yield. The upconversion composition utilizing perylene monoimide is capable of utilizing more than 12% of the generated triplet states to generate emissive, excited singlet states under one sun illumination, potentially enhancing the energy conversion efficiency of high band gap solar cells.
ENERGY & ENVIRONMENTAL SCIENCE
(2021)
Review
Chemistry, Physical
Jiale Feng, Jessica Alves, Damon M. de Clercq, TimothyW. Schmidt
Summary: This review addresses the physicochemical phenomena, kinetics, and design requirements of photochemical upconversion, as well as the spin physics of bi-excitonic interactions and light-matter coupling phenomena that could enhance the process.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Jihao Jin, Tianjun Yu, Jinping Chen, Rui Hu, Guoqiang Yang, Yi Zeng, Yi Li
Summary: Triplet-triplet annihilation upconversion (TTA-UC) is a promising technology that can convert low-energy photons to high-energy photons under low excitation intensity and incoherent light source. It has shown great potential in solar cells, photocatalysis, 3D printing, smart luminescence materials, and biological applications. This review focuses on the advances of TTA-UC in the application of photochemical transformation, particularly in photocatalytic production of solar fuels and high value-added compounds, as well as the emerging photochemical preparation of organics and polymers. The value of TTA-UC approaches in these contexts is summarized, and future challenges and potential strategies are discussed.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Felix Glaser, Oliver S. Wenger
Summary: Combining the energy input from two red photons allows for chemical reactions that would normally require blue or ultraviolet irradiation. This biphotonic excitation strategy offers advantages such as deeper penetration and less photo-damage. By altering the photosensitizer in a dual photocatalytic system, the reaction outcome can be completely altered. Different biphotonic mechanisms lead to different photochemical reactivities, which can be controlled by changing the photosensitizer.
Article
Chemistry, Multidisciplinary
Mo Yang, Sara Sheykhi, Yu Zhang, Carsten Milsmann, Felix N. Castellano
Summary: The study demonstrates efficient photochemical upconversion using a Zr(iv) LMCT complex as a triplet photosensitizer and various acceptor/annihilators in THF solutions. The research shows high TTET and TTA processes with impressive record-setting UC efficiencies achieved under optimized conditions. This emphasizes the importance of developing molecular-based triplet photosensitizers based on earth-abundant metals.
Article
Engineering, Environmental
Xinyu Wang, Xing Wang, Glib Baryshnikov, Rashid R. Valiev, Rongwei Fan, Songtao Lu, Hans Agren, Guanying Chen
Summary: Triplet fusion upconversion is a versatile technology with applications in various fields, and the combination of organic infrared dyes with inorganic lanthanide nanocrystals in this study has shown promising results in enhancing energy conversion efficiency and achieving effective triplet fusion upconversion.
CHEMICAL ENGINEERING JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Tracy Schloemer, Pournima Narayanan, Qi Zhou, Emma Belliveau, Michael Seitz, Daniel N. Congreve
Summary: Using light to control matter has long been a goal for scientists, and triplet-triplet annihilation upconversion (TTA-UC) may provide a solution by converting low energy photons to high energy photons. This process allows for precise generation of high energy photons, overcoming challenges of light attenuation. Researchers are exploring various sensitizers and annihilators for TTA-UC in solution and solid-state applications. This review discusses deployment strategies and recent examples of TTA-UC, identifying critical needs to advance it from an academic curiosity to a scalable technology.
Article
Polymer Science
Aurore Caron, Guillaume Noirbent, Didier Gigmes, Frederic Dumur, Jacques Lalevee
Summary: A novel perspective for free radical polymerization of acrylate-based monomers using triplet-triplet annihilation upconversion (TTA-UC) without heavy metal catalysts is proposed. Experimental results suggest a competition between TTA-UC and NIR photothermal activation, with the photothermal effect seeming to be more efficient.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Roslyn Forecast, Francesco Campaioli, Timothy W. Schmidt, Jared H. Cole
Summary: Upconversion processes convert multiple low energy photons into one higher energy photon and have potential applications in photovoltaics and biomedicine. This study focuses on two specific mechanisms for photochemical upconversion in solution: triplet-triplet annihilation (TTA) and singlet oxygen mediated energy transfer (SOMET). A kinetic model is developed to explain the different photoluminescence profiles of oxygenated and deoxygenated systems, and the triplet-triplet annihilation rate constant is estimated from the magnetic field response. Design principles to maximize upconversion photoluminescence intensity in oxygenated solution are determined.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Materials Science, Multidisciplinary
Jussi Isokuortti, Iiro Kiiski, Tiina Sikanen, Nikita Durandin, Timo Laaksonen
Summary: The potential of triplet fusion photon upconversion (TF-UC) in biomedicine and life sciences is restricted by its sensitivity to oxygen. This study demonstrates the use of microfluidic chips made of oxygen depleting materials to evaluate the oxygen tolerability of different nanocarriers in physiological oxygen levels. The addition of oxygen scavengers in the nanocarrier's oil phase significantly improves their ability to tolerate oxygen.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Review
Chemistry, Inorganic & Nuclear
Colm Healy, Lily Hermanspahn, Paul E. Kruger
Summary: Photon upconversion through self-assembled materials requires efficient triplet exciton migration. This promising area of research will benefit greatly from a wider range of sensitiser-annihilator pairs to expand the applicability of these materials.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Yifan Bo, Yuxuan Hou, Dominik Thiel, Renee Weiss, Timothy Clark, Michael J. Ferguson, Rik R. Tykwinski, Dirk M. Guldi
Summary: This study designs two tetracene dimers with different linking modes, and characterizes the interplay between intramolecular singlet fission (intra-SF) and intramolecular triplet-triplet annihilation up-conversion (intra-TTA-UC) through steady-state and time-resolved absorption and fluorescence spectroscopy. By using Pd-phthalocyanine as a sensitizer, intra-TTA-UC is achieved in the two dimers via indirect photoexcitation in the near-infrared part of the solar spectrum. Temperature-dependent measurements reveal the impact of thermal effects on intra-SF and intra-TTA-UC in different dimers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Reynolds Dziobek-Garrett, Christian J. Imperiale, Mark W. B. Wilson, Thomas J. Kempa
Summary: Engineered energy transfer processes in van der Waals heterostructures can be achieved by utilizing atomically abrupt, angstrom-scale, and topologically tailorable interfaces. This study demonstrates the fabrication of heterostructures composed of 2D WSe2 monolayers interfaced with DBP-doped rubrene using vapor deposition methods. Photon upconversion is observed through rapid quenching of WSe2 emission by rubrene and fluorescence from DBP molecules. The upconversion emission efficiency is maximized at low excitation intensities, indicating a triplet fusion mechanism. This research highlights the potential for advanced optoelectronic applications utilizing van derWaals heterostructures.
Article
Chemistry, Multidisciplinary
Rinat Meir, Tal Hirschhorn, Sungsoo Kim, Kealan J. Fallon, Emily M. Churchill, Dino Wu, Hee Won Yang, Brent R. Stockwell, Luis M. Campos
Summary: The ability to optically induce biological responses in 3D has been limited by the penetration of visible light, but hydrogels that convert red or near-IR light into blue light have been developed to trigger photochemical responses. This approach allows for precise control of cell function and may lead to new biochemical applications.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Materials Science, Multidisciplinary
Lin-Han Jiang, Le Zeng, Ming-Yu Zhang, Ling Huang, Dai-Wen Pang
Summary: This study presents a new strategy to modulate the triplet state of BODIPY by implementing non-conjugated n-pi spatial electron coupling, which realizes efficient near-infrared light-activable triplet fusion upconversion in both solution and solid-state materials. The implementation of this strategy has significant potential applications in various fields, such as photoredox catalysis, photodynamic therapy, and photovoltaic devices.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Can Gao, Atul Shukla, Haikuo Gao, Zhagen Miao, Yihan Zhang, Pu Wang, Guiwen Luo, Yi Zeng, Wallace W. H. Wong, Trevor A. Smith, Shih-Chun Lo, Wenping Hu, Ebinazar B. Namdas, Huanli Dong
Summary: Organic light-emitting transistors (OLETs) have demonstrated great potential applications in various fields as highly integrated and minimized optoelectronic devices. However, the construction of high-performance OLETs remains a significant long-term challenge, especially for single component active layer OLETs. In this study, the successful harvesting of triplet excitons in a high mobility emissive molecule, 2,6-diphenylanthracene (DPA), through the triplet-triplet annihilation process is demonstrated.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Anjay Manian, Rohan J. Hudson, Pria Ramkissoon, Trevor A. Smith, Salvy P. Russo
Summary: This benchmarking study investigates non adiabatic matrix coupling elements (NACMEs) using different density functionals, with a focus on the photophysical properties of perylene in toluene. The study compares theoretical calculations with experimental results, deriving relations between TDDFT and DFT/MRCI properties and identifying the most promising data sets.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Organic
Paulo Miguel Simon, Jonathan O. Castillo, Tze Cin Owyong, Jonathan M. White, Nicolau Saker Neto, Wallace W. H. Wong
Summary: Boronic acid protecting group chemistry significantly expands the versatility of Suzuki-Miyaura cross-coupling. The BOMA ligand, similar to the MIDA ligand, forms tridentate complexes with boronic acids, but can be deprotected using organic acids. BOMA boronates exhibit excellent stability in both alkaline and acidic conditions, enabling a wide range of chemoselective reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Na Wu, Nicholas Kirkwood, Nicolau Saker Neto, Rehana Pervin, Paul Mulvaney, Wallace W. H. Wong
Summary: To understand the factors controlling energy transfer from QDs to dyes, a series of CdxZn1-xS/ZnS QD-PDI composite nanocrystals were fabricated. The maximum energy transfer efficiency of 91% was achieved with composites containing carboxylic acid anchoring groups and longer alkyl chains. Composites with carboxylic acid anchors exhibited greater photostability compared to those with amine anchors.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Review
Materials Science, Multidisciplinary
Zicheng Li, Bolong Zhang, Zhihao Zhang, Jean-Claude Buenzli, Abd Rashid bin Mohd Yusoff, Yong-Young Noh, Peng Gao
Summary: Metal-halide perovskites-based optoelectronic devices, such as solar cells and LEDs, have become direct competitors to established technologies due to their cost-effectiveness. However, their development is still limited by narrow absorption band, low charge carrier mobility, energy level mismatching, and poor stability. Lanthanides have been applied to overcome these limitations. This article provides a review of the history and recent developments in lanthanide materials for perovskite optoelectronic devices.
MATERIALS SCIENCE & ENGINEERING R-REPORTS
(2023)
Article
Physics, Multidisciplinary
Subhajit Chakraborty, Yang Xu, Ann Roberts, Debabrata Goswami, Trevor A. Smith
Summary: Evanescent wave-induced fluorescence spectroscopy (EWIFS) is a widely used technique for studying complex media in physical, chemical, and biological sciences. It utilizes the evanescent wave generated by total internal reflection to probe the photoluminescence characteristics of the sample. However, it faces limitations in imaging samples with higher refractive indices.
Article
Chemistry, Physical
Roslyn Forecast, Elham M. Gholizadeh, Shyamal K. K. Prasad, Simon Blacket, Patrick C. Tapping, Dane R. McCamey, Murad J. Y. Tayebjee, David M. Huang, Jared H. Cole, Timothy W. Schmidt
Summary: The magnetic field dependence of triplet fusion can be used to determine the parameters of triplet fusion collisions. The reduction of magnetic field effect for perylene triplet fusion is observed as the system moves from quadratic to linear annihilation regimes with an increase in laser power. This approach can be applied to screen potential annihilators for photon upconversion.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Physics, Multidisciplinary
Miles I. Collins, Francesco Campaioli, Murad J. Y. Tayebjee, Jared H. Cole, Dane R. McCamey
Summary: Singlet fission refers to the production of two triplet excitons from one singlet exciton while conserving spin. Although the presence of a spin-2 (quintet) triplet-pair state resulting from singlet fission is well established, the exact mechanism for quintet formation has not been determined, making the design of materials for optimal quintet formation challenging. In this study, the authors propose a mechanism in which fluctuations in inter-triplet exchange coupling drive rapid and efficient quintet formation. They demonstrate that quintet formation is feasible even in the strong-exchange regime, consistent with recent experimental predictions. Evaluating the performance of this quintet formation mechanism under different conformational freedom scenarios, the authors establish a connection between quintet dynamics and material properties of singlet fission molecules.
COMMUNICATIONS PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Bolong Zhang, Kieran D. Richards, Beatrice E. Jones, Abigail R. Collins, Rosie Sanders, Sarah R. Needham, Pu Qian, Amoghavarsha Mahadevegowda, Caterina Ducati, Stanley W. Botchway, Rachel C. Evans
Summary: This study demonstrates the first example of triplet-triplet annihilation upconversion (TTA-UC) based lifetime imaging microscopy. Ultra-small nanoparticle (NP) probes were used to overcome background autofluorescence and achieve excellent image contrast and oxygen mapping in living cells.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Anjay Manian, Francesco Campaioli, Rohan J. Hudson, Jared H. Cole, Timothy W. Schmidt, Igor Lyskov, Trevor A. Smith, Salvy P. Russo
Summary: The role of charge transfer states in multi-exciton mechanisms is difficult to model accurately, but the intermolecular packing has been shown to heavily influence these mechanisms. By studying a gas phase perylene dimer, it was found that displaced geometries yield large charge transfer contributions for singlet fission, while triplet-triplet annihilation charge transfer couplings are weak. Slipping of the dimer cofacial geometry is beneficial to both charge transfer-mediated processes within a wavefunction overlap scheme. The results provide insights into singlet fission and can guide further investigations in this field.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Trevor A. Smith, Rohan J. Hudson, Anjay Manian, Christopher R. Hall, Timothy W. Schmidt, Salvy P. Russo, Kenneth P. Ghiggino
Summary: Gating logical operations through high-lying excited states of perylene has potential for the development of ultrafast, subnanometer computational devices. This study uses femtosecond spectroscopy and quantum chemical calculations to investigate the relaxation dynamics of monomeric perylene's higher electronic excited states. The obtained lifetimes of the 2(1)Ag and 2(1)B(2u) states suggest that these states could be useful for logical operations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Thomas S. C. MacDonald, Murad J. Y. Tayebjee, Miles I. Collins, Elango Kumarasamy, Samuel N. Sanders, Matthew Y. Sfeir, Luis M. Campos, Dane R. McCamey
Summary: In this report, the use of continuous-wave and pulsed electron spin resonance techniques to study the properties of triplet-pair states is demonstrated. It is found that the generation rate of high-spin triplet pairs is dependent on the molecular orientation and the static magnetic field. This finding is important for materials design and applications in photovoltaics, information technologies, and biomedical imaging.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yixiong Ji, Wangxian Chen, Di Yan, James Bullock, Yang Xu, Zhenghua Su, Wentong Yang, Jamie Stuart Laird, Tian Zheng, Na Wu, Wusong Zha, Qun Luo, Chang-Qi Ma, Trevor A. Smith, Fangyang Liu, Paul Mulvaney
Summary: Photovoltaic thin film solar cells based on CZTSSe have limited efficiency due to the deficit in open circuit voltage. The proposed ZAZA window structure offers improved optoelectronic properties and carrier collection efficiency, resulting in a significant enhancement of VOC. These advances enable the fabrication of high-efficiency CZTSSe solar cells without the need for an anti-reflective coating.
Article
Chemistry, Physical
Benjamin A. Laws, Olha Krechkivska, Klaas Nauta, Scott H. Kable, Timothy W. Schmidt
Summary: Excitation spectra of protonated and deuteronated anthracene were obtained using triple-resonance dissociation spectroscopy. Very cold cations, protonated/deuteronated exclusively at the 9-position, were generated from two-colour two-photon threshold ionisation of 9-dihydroanthracenyl radicals (C14H11). The excitation spectra revealed rich structure, not previously resolved, which was assigned based on anharmonic and Herzberg-Teller coupling calculations. This study showed that excitation of protonated anthracene induces a symmetry-breaking intramolecular charge-transfer process, with the positively charged hole hopping from the central bridging sp(2) carbon onto one of the aromatic rings. Signatures of this charge-transfer event were observed in the excitation spectrum through active Herzberg-Teller progressions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)