I shrugged. “I know that now, or I think I do. But when I was a young girl, Father always blamed me or Mother when something went wrong, and so did my brothers even when they had messed up, and I believed them. If you’re told something often enough, you just take it for the truth. When Father hit me, I thought I deserved it.” Qi, F. et al. Photodissociation of ethylene sulfide at 193 nm: a photofragment translational spectroscopy study with VUV synchrotron radiation and ab initio calculations. J. Am. Chem. Soc. 123, 148–161 (2001). Barclay, T. M. et al. The heterocyclic diradical benzo-1,2:4,5-bis(1,3,2-dithiazolyl). electronic, molecular and solid state structure. J. Am. Chem. Soc. 119, 2633–2641 (1997). Sandström, J. Static and dynamic stereochemistry of push-pull and strained ethylenes. Top. Stereochem. 14, 83–181 (1983). I shook my head. Nobody had bothered telling me the details. I wasn’t sure if it was to protect me, or because they thought I had no right to know as a mere girl. I bet my brothers knew. “I thought Luca shot him.”

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Shvo, Y. & Shanan-Atidi, H. Internal rotation in olefins. I. Kinetic investigation by nuclear magnetic resonance. J. Am. Chem. Soc. 91, 6683–6689 (1969). Kang, HW., Liu, YC., Shao, WK. et al. Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[ a, i]fluorenylidene) and its derivatives. Department of Medical and Applied Chemistry, Kaohsiung Medical University, 80708, Kaohsiung, Taiwan Saltiel, J. & Charlton, J. L. Cis-trans isomerization of olefins in Rearrangements in Ground and Excited States (ed. de Mayo, P.), Vol. 3, 25–89 (Academic Press, New York, 1980).Gong, X. et al. Bulk heterojunction solar cells with large open-circuit voltage: electron transfer with small donor-acceptor energy offset. Adv. Mater. 23, 2272–2277 (2011). Schröder, K. et al. Tetrabenzo[ a,c,g,i]fluorenyllithium and η 5-tetrabenzo[ a,c,g,i]fluorenyl-titanium complexes. Organometallics 25, 3824–3836 (2006). Liu, J. et al. Open-shell nonbenzenoid nanographenes containing two pairs of pentagonal and heptagonal rings. J. Am. Chem. Soc. 141, 12011–12020 (2019). I smiled, couldn’t help it. It felt like a weight had been lifted off my chest, as if everything I hadn’t even dared to dream, much less hope for, was suddenly in my reach.

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Tschitschibabin, A. E. Über einige phenylierte derivate des p,p-Ditolyls. Ber. Dtsch. Chem. Ges. 40, 1810–1819 (1907). Compounds 1a– d, 2, and 3 were prepared from 7a– 7d, 8 and 9, respectively, by the tBuOK-mediated oxidative dehydrogenation. The reaction conditions were substrate dependent. For details, see Supplementary Information. Characterization

Barham, J. P. et al. KO tBu: A privileged reagent for electron transfer reactions? J. Am. Chem. Soc. 138, 7402–7410 (2016). Y.T.W. conceived the idea and designed the experiments. H.W.K. undertook the synthesis and analysis of all compounds, as well as the measurement of photoabsorption and electrochemical properties. M.H.C. directed investigations of magnetic properties. Y.C.L. conducted the ESR and SQUID measurements. M.J.C. provided guidance for the computational studies, while C.T.H. and W.K.S. executed the DFT calculations. P.T.C. and S.D.Y. supervised photodynamic investigations. B.H.C., C.H.L. and Y.C.W. measured the TA spectra and analyzed data. M.H.C, P.T.C. and Y.T.W. co-wrote the manuscript. All authors discussed the results and commented on the manuscript. Corresponding authors

Twisted Bonds: the spellbinding conclusion to the These Twisted Bonds: the spellbinding conclusion to the

Eaton, S. S., More, K. M., Sawant, B. M. & Eaton, G. R. J. Use of the ESR half-field transition to determine the interspin distance and the orientation of the interspin vector in systems with two unpaired electrons. J. Am. Chem. Soc. 105, 6560–6567 (1983). Bleaney, B. & Bowers, K. D. Anomalous paramagnetism of copper acetate. Proc. R. Soc. London Ser. A 214, 451–465 (1952). Kanawati, B., Genest, A., Schmitt-Kopplin, P. & Lenoir, D. Bis-dibenzo[a.i]fluorenylidene, does it exist as stable 1,2-diradical? J. Mol. Model. 18, 5089–5095 (2012).

Kawata, S. et al. Controlling the excited-state energy levels of 9,9′-bifluorenylidene derivatives by twisting their structure to attaining singlet fission character in organic photovoltaics. J. Mater. Chem. C 5, 4909–4914 (2017). Francl, M. M. et al. Self‐consistent molecular orbital methods. A polarization‐type basis set for second‐row elements. XXIII. J. Chem. Phys. 77, 3654 (1982). Escher, A., Rutsch, W. & Neuenschwander, M. Synthese von Pentafulvalen durch oxidative Kupplung von Cyclopentadienid mittels Kupfer(II)-chlorid. Helv. Chim. Acta 69, 1644–1654 (1986). Synthesis, structural analysis, and properties of highly twisted alkenes 13,13’-bis(dibenzo[ a, i]fluorenylidene) and its derivatives Father occasionally made it their task to discipline me, yes. They are seven and nine years older than me, so…” I considered Nino’s expression. “Nino,” I said quietly but firmly. “I don’t want you to kill them because of what they did when they were children.”

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Nishiuchi, T., Aibara, S., Sato, H. & Kubo, T. Synthesis of π‐extended Thiele’s and Chichibabin’s hydrocarbons and effect of the π‐congestion on conformations and electronic states. J. Am. Chem. Soc. 144, 7479–7488 (2022). Conyard, J. et al. Ultrafast excited state dynamics in 9,9′-bifluorenylidene. J. Phys. Chem. A 118, 5961–5968 (2014).

VT 1H NMR experiments using unsymmetrical compounds 1d (183–303 K) and 2 (183–413 K) were performed (see Supplementary Information p. 43 and 45). Upon cooling, the signals exhibited progressive line sharpening without any significant decoalescence. The phenomenon is most likely due to the following three possibilities: (1) identical resonances of the syn- and anti-isomers, (2) the amount of energetically unstable isomer being too low to be detected, and (3) the C = C bond rotational rate at 183 K being faster than the timescale of 1H NMR spectroscopy. The first two options are unlikely, and the energy difference between the two isomers is less than 0.13 kcal/mol (see Supplementary Information p. 33), which results in an unstable isomer with a Boltzmann population greater than 40% at 183 K. In the VT 1H NMR spectra of 3, peaks with progressive line broadening were observed at temperatures higher than 303 K. Magnetic properties H={E}_{{{{{{\rm{elec}}}}}}}+{{{{{\rm{ZPE}}}}}}+({H}_{{{{{{\rm{vib}}}}}}}+{H}_{{{{{{\rm{trans}}}}}}}+{H}_{{{{{{\rm{rot}}}}}}}+{{{{{\rm{RT}}}}}})\) Cyclic voltammetry Except for T 1-( M, M)- 3 ( θ 1 = 74°, θ 2 = 22°), the T 1 state of the studied compounds exhibits a perpendicular conformation ( θ 1 = 86° or 90°) with an elongated bond d (1.462–1.466 Å) and (nearly) planar DBF moieties ( θ 2 = 0°; 8° for T 1- 2). The Δ H STs obtained by DFT calculations are as folows: ( M, M)- 3 (5.79 kcal/mol, see Table 2) > 1a (5.52 kcal/mol) > 1c (5.41 kcal/mol) > 1d (4.26 kcal/mol) ≈ 2 (4.33 kcal/mol) > 1b (3.19 kcal/mol). The low Δ H STs for 1b and 1d most likely originate from additional stabilization of π-extended alkynyl moieties on T 1- 1b and T 1- 1d, respectively, as shown in their spin density plots (see below and Supplementary Fig. 10). In most cases, the molecular geometries of the TS rot and T 1 states are (nearly) identical (see Supplementary Table 2). Structural parameters of ( M, M)- 3-TS rot ( θ 1 = 82°, θ 2 = 19°, θ 3 = 41°, d = 1.462 Å) and T 1-( M, M)- 3 ( θ 1 = 74°, θ 2 = 22°, θ 3 = 42°, d = 1.462 Å) are slightly different, and their DBF moieties are highly twisted. The Δ H ‡ rots of the studied compounds were determined to be 2.35–5.13 kcal/mol (Table 2), indicating that the rotation of the C = C bond can be as facile as that of an aryl-aryl bond in a simple biphenyl, such as 2-flourobiphenyl (Δ G ‡ rot 4.4 kcal/mol 40). Photophysical properties Dupeyre, R. M., Rassat, A. & Ronzaud, J. Nitroxides. LII. Synthesis and electron spin resonance studies of N, N’-dioxy-2,6-diazaadamantane, a symmetrical ground state triplet. J. Am. Chem. Soc. 96, 6559–6568 (1974).