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1. Benzobisthiadiazole-based high-spin donor–acceptor conjugated polymers with localized spin distribution

   https://doi.org/10.1039/D1MA00144B  

   Sabuj, Md Abdus; Huda, Md Masrul; Sarap, Chandra Shekar; Rai, Neeraj (May 2021, Materials Advances)

   null (Ed.)

   Stable organic semiconductors (OSCs) with a high-spin ground-state can profoundly impact emerging technologies such as organic magnetism, spintronics, and medical imaging. Over the last decade, there has been a significant effort to design π-conjugated materials with unpaired spin centers. Here, we report new donor–acceptor (D–A) conjugated polymers comprising cyclopentadithiophene and cyclopentadiselenophene donors with benzobisthiadiazole (BBT) and iso-BBT acceptors. Density functional theory calculations show that the BBT-based polymers display a decreasing singlet–triplet energy gap with increasing oligomer chain length, with degenerate singlet and triplet states for a N = 8 repeat unit. Furthermore, a considerable distance between the unpaired electrons with a pure diradical character disrupts the π-bond covalency and localizes the unpaired spins at the polymer ends. However, replacing the BBT acceptor with iso-BBT leads to a closed-shell configuration with a low-spin ground-state and a localized spin density on the polymer cores. This study shows the significance of the judicious choice of π-conjugated scaffolds in generating low- ( S = 0) and high-spin ( S = 1) ground-states in the neutral form, by modulation of spin topology in extended π-conjugated D–A polymers for emergent optoelectronic applications. 

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2. Room-temperature quantum sensing with photoexcited triplet electrons in organic crystals

   https://doi.org/10.1103/PhysRevResearch.7.013192  

   Singh, Harpreet; D'Souza, Noella; Zhong, Keyuan; Druga, Emanuel; Oshiro, Julianne; Blankenship, Brian; Montis, Riccardo; Reimer, Jeffrey A; Breeze, Jonathan D; Ajoy, Ashok (February 2025, Physical Review Research)

   Quantum sensors have notably advanced high-sensitivity magnetic field detection. Here, we report quantum sensors constructed from polarized spin-triplet electrons in photoexcited organic chromophores, specifically focusing on pentacene-doped para-terphenyl $(\approx 0.1\%)$. We demonstrate essential quantum sensing properties at room temperature (RT): optically generated electronic polarization and state-dependent fluorescence contrast by leveraging differential pumping and relaxation rates between triplet and ground states. We measure high optically detected magnetic resonance contrast $\approx 16.8\%$of the triplet states at RT, along with long coherence times under spin echo and Carr-Purcell-Meiboom-Gill (CPMG) sequences, $T_2=2.7\mu \mathrm{s}$and $T_2^{\text{DD}}=18.4\mu \mathrm{s}$, respectively, limited only by the triplet lifetimes. The material offers several advantages for quantum sensing, including the ability to grow large (cm scale) crystals at low cost, absence of paramagnetic impurities, and electronic diamagnetism when not optically illuminated. Utilizing pentacene as a representative of a broader class of spin triplet- polarizable organic molecules, this paper highlights the potential for quantum sensing in chemical systems. 

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3. Photochemistry of carbon nitrides and heptazine derivatives

   https://doi.org/10.1039/D1CC02745J  

   Hwang, Doyk; Schlenker, Cody W. (September 2021, Chemical Communications)

   We explore the photochemistry of polymeric carbon nitride (C 3 N 4 ), an archetypal organic photocatalyst, and derivatives of its structural monomer unit, heptazine (Hz). Through spectroscopic studies and computational analysis, we have observed that Hz derivatives can engage in non-innocent hydrogen bonding interactions with hydroxylic species. The photochemistry of these complexes is influenced by intermolecular nπ*/ππ* mixing of non-bonding orbitals of each component and the relative energy of intermolecular charge-transfer (CT) states. Coupling of the former to the latter appears to facilitate proton-coupled electron transfer (PCET), resulting in biradical products. We have also observed that Hz derivatives exhibit an extremely rare inverted singlet/triplet energy splitting (Δ E ST ). In violation of Hund's multiplicity rules, the lowest energy singlet (S 1 ) is stabilized relative to the lowest triplet (T 1 ) electronic excited state. Exploiting this unique inverted Δ E ST character has obvious implications for transformational discoveries in solid-state OLED lighting and photovoltaics. Harnessing this inverted Δ E ST , paired with light-driven intermolecular PCET reactions, may enable molecular transformations relevant for applications ranging from solar energy storage to new classes of non-triplet photoredox catalysts for pharmaceutical development. To this end, we have explored the possibility of optically controlling the photochemistry of Hz derivatives using ultrafast pump–push–probe spectroscopy. In this case, the excited state branching ratios among locally excited states of the chromophore and the reactive intermolecular CT state can be manipulated with an appropriate secondary “push” excitation pulse. These results indicate that we can predictively redirect chemical reactivity with light in this system, which is an avidly sought achievement in the field of photochemistry. Looking forward, we anticipate future opportunities for controlling heptazine photochemistry, including manipulating PCET reactivity with a diverse array of substrates and optically delivering reducing equivalents with, for example, water as a partial source of electrons and protons. Furthermore, we wholly expect that, over the next decade, materials such as Hz derivatives, that exhibit inverted Δ E ST character, will spawn a significant new research effort in the field of thin-film optoelectronics, where controlling recombination via triplet excitonic states can play a critical role in determining device performance. 

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4. Ground-State Charge-Transfer Doping Interactions in Donor–Acceptor Semiconducting Polymers

   https://doi.org/10.26434/chemrxiv-2025-g7tb5  

   Mahalingam, Paramasivam; Smith, Tanner; Balandin, Tanya; Gupta, Debapriya; Yu, Siqi; Dalal, Pushkar; Ng, Tse Nga; Flood, Amar Hugh; Danielsen, Scott_P O; Azoulay, Jason David (June 2025, ChemRxiv)

   Conjugated polymers are at the heart of numerous current and emerging technologies. Doping, a process by which charge carriers are introduced, is crucial to their functionality and performance. Despite significant historical context and the exploration of a broad chemical space, doping processes that are activated by formation of a ground-state charge-transfer complex (GS-CTC), which is mediated by the supramolecular hybridization between the frontier molecular orbitals of distinct molecular species, remain poorly understood. There are no clear demonstrations of this phenomena in contemporary donor–acceptor (DA) conjugated polymers (CP). Here, using diketopyrrolopyrrole-based donor–acceptor semiconducting polymers and a -conjugated penta-t-butylpentacyanopentabenzo[25]annulene “cyanostar” macrocycle, we demonstrate the first examples of features that control GS-CTC formation in contemporary DA CP frameworks. Using complementary experimental techniques and theory, we articulate how subtle molecular, electronic, and solid-state features impact supramolecular hybridization of the frontier molecular orbitals and impact the resultant (opto)electronic, magnetic, and transport properties. These studies demonstrate that subtle effects arising from the admixture between distinct -conjugated materials can have dramatic outcomes on properties and performance through modification of the density of states (DOS). These results will enable completely new design rules for organic semiconductors with precise property control. 

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5. A high-spin ground-state donor-acceptor conjugated polymer

   https://doi.org/10.1126/sciadv.aav2336  

   London, A. E.; Chen, H.; Sabuj, M. A.; Tropp, J.; Saghayezhian, M.; Eedugurala, N.; Zhang, B. A.; Liu, Y.; Gu, X.; Wong, B. M.; et al (May 2019, Science Advances)

   Interest in high-spin organic materials is driven by opportunities to enable far-reaching fundamental science and develop technologies that integrate light element spin, magnetic, and quantum functionalities. Although extensively studied, the intrinsic instability of these materials complicates synthesis and precludes an understanding of how fundamental properties associated with the nature of the chemical bond and electron pairing in organic materials systems manifest in practical applications. Here, we demonstrate a conjugated polymer semiconductor, based on alternating cyclopentadithiophene and thiadiazoloquinoxaline units, that is a ground-state triplet in its neutral form. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-to-low spin energy gap of 9.30 × 10 −3 kcal mol −1 . The strongly correlated electronic structure, very narrow bandgap, intramolecular ferromagnetic coupling, high electrical conductivity, solution processability, and robust stability open access to a broad variety of technologically relevant applications once thought of as beyond the current scope of organic semiconductors. 

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