Photochemically assisted synthesis of phenacenes fluorinated at the terminal benzene rings and their electronic spectra

• Yuuki Ishii,
• Minoru Yamaji,
• Fumito Tani,
• Kenta Goto,
• Yoshihiro Kubozono and
• Hideki Okamoto

Beilstein J. Org. Chem. 2025, 21, 670–679, doi:10.3762/bjoc.21.53

• wavelength region for the corresponding parent phenacenes whereas their fluorescence bands markedly red-shifted and broadened. These observations suggest that the intermolecular interactions of excited-state F8-phenacene molecules are significantly different from those of the corresponding parent molecules

• negative (orange region) in the parent compounds, whereas the phenacene cores turned to be positive (blue) for the F8-phenacenes. Therefore, one can manipulate the polarization of the phenacene cores through the introduction of fluorine atoms without altering the electronic spectral features. The excited

• -state electronic characteristics were also calculated, and the electronic transitions for the first two vertical absorption bands are summarized in Table 2. Although the calculated S1←S0 and S2←S0 electronic transition energies were slightly overestimated to show a systematic difference between the

Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye

• Metodej Dvoracek,
• Brendan Twamley,
• Mathias O. Senge and
• Mikhail A. Filatov

Beilstein J. Org. Chem. 2025, 21, 500–509, doi:10.3762/bjoc.21.37

• )bimane (DMOCDO10) and syn-(Me,Me)bimane (DXABIM10) [26], a room temperature structure of Me4B (TNZBCO10) [27], and a planar syn-(H,ethynyl)bimane (WAYHEJ) [28]. Optical properties The optical properties of the three bimanes were measured to investigate differences in their excited state properties, as

• proposed pathway begins with the excitation of a bimane molecule to its singlet-excited state, followed by intersystem crossing (ISC) to the triplet state. The triplet state then forms an excimer complex with a neighboring bimane molecule, leading to the formation of a single bond and generating a triplet

Synthesis, structure, ionochromic and cytotoxic properties of new 2-(indolin-2-yl)-1,3-tropolones

• Yurii A. Sayapin,
• Eugeny A. Gusakov,
• Inna O. Tupaeva,
• Alexander D. Dubonosov,
• Igor V. Dorogan,
• Valery V. Tkachev,
• Anna S. Goncharova,
• Gennady V. Shilov,
• Natalia S. Kuznetsova,
• Svetlana Y. Filippova,
• Tatyana A. Krasnikova,
• Yanis A. Boumber,
• Alexey Y. Maksimov,
• Sergey M. Aldoshin and
• Vladimir I. Minkin

Beilstein J. Org. Chem. 2025, 21, 358–368, doi:10.3762/bjoc.21.26

• the 7,8 (OH) form and is caused by the excited-state intramolecular proton transfer (ESIPT) process due to intramolecular O→N proton migration in the singlet excited state [26][27]. The ionochromic sensitivity of compounds 7a,b and 8a,b to anions was investigated in acetonitrile upon addition of tetra

Red light excitation: illuminating photocatalysis in a new spectrum

• Lucas Fortier,
• Corentin Lefebvre and
• Norbert Hoffmann

Beilstein J. Org. Chem. 2025, 21, 296–326, doi:10.3762/bjoc.21.22

• , where the low-lying excited state often corresponds to the metal-to-ligand charge transfer (MLCT) transition. As the atomic number increases, relativistic effects become more pronounced, leading to the contraction of s and p orbitals while the d and f orbitals expand and become more diffuse. While these

• excitation to the triplet state from the ground state S0. This effect mitigates rapid back-electron transfer from the singlet excited state to the ground state, extending the excited-state lifetime of the photocatalyst. Since the T1 → S0 transition is spin-forbidden, the process increases the overall

• study, the authors have developed a complementary ground-state- and excited-state-driven aryl oxidative addition platform based on an N,C,N-bismuthinidene complex, showing the unique capacity of this main-group element to engage in reactivity typically associated with d-block metals [21]. The study

Synthesis, structure and π-expansion of tris(4,5-dehydro-2,3:6,7-dibenzotropone)

• Yongming Xiong,
• Xue Lin Ma,
• Shilong Su and
• Qian Miao

Beilstein J. Org. Chem. 2025, 21, 1–7, doi:10.3762/bjoc.21.1

• in 3, which consume the energy of the excited state. Figure 4 shows the UV–vis absorption spectrum of 3 in cyclohexane with the absorption edge at 561 nm and its emission spectrum with a peak at 580 nm. In the test windows of cyclic voltammetry (Supporting Information File 1, Figure S1), 3 exhibits

Synthesis, characterization, and photophysical properties of novel 9‑phenyl-9-phosphafluorene oxide derivatives

• Shuxian Qiu,
• Duan Dong,
• Jiahui Li,
• Huiting Wen,
• Jinpeng Li,
• Yu Yang,
• Shengxian Zhai and
• Xingyuan Gao

Beilstein J. Org. Chem. 2024, 20, 3299–3305, doi:10.3762/bjoc.20.274

• the CT feature in the excited state. Further, the solvent dependence of 7-H exhibits good consistence with that reported by the Nishida group [31]. The PLQY and τDF values of the PhFlOP-based emitters 7 were measured in degassed toluene, and the corresponding data are included in Table 2, showing a

Advances in the use of metal-free tetrapyrrolic macrocycles as catalysts

• Mandeep K. Chahal

Beilstein J. Org. Chem. 2024, 20, 3085–3112, doi:10.3762/bjoc.20.257

• to absorb significant amounts of visible light photons, which allows them to reach an excited state. The excited porphyrin molecule is likely to undergo energy transfer (ET; photosensitization) or single-electron transfer (SET; photoredox catalysis) to substrate molecules (Figure 13). In

• photochemistry, porphyrins are mainly used for the generation of singlet oxygen (1O2) or other reactive oxygen species. Porphyrins in the triplet excited state can relax to the ground state by transferring energy to molecular oxygen (triplet state) forming 1O2 (Figure 13b) [67]. Photosensitized singlet oxygen

• initiated the reaction pathway. The authors proposed that under light irradiation, the porphyrin transitioned to its excited state, generating a phenyl radical through photoinduced single-electron transfer (Figure 15c). This phenyl radical then added to the furan (heteroarene), forming an aryl radical

Extension of the π-system of monoaryl-substituted norbornadienes with acetylene bridges: influence on the photochemical conversion and storage of light energy

• Robin Schulte,
• Dustin Schade,
• Thomas Paululat,
• Till J. B. Zähringer,
• Christoph Kerzig and
• Heiko Ihmels

Beilstein J. Org. Chem. 2024, 20, 3061–3068, doi:10.3762/bjoc.20.254

• ones. This lack of correlation may indicate that several different factors and processes contribute to different extent to the course of the photoreaction, for example, steric hindrance and resulting torsion angles between the arene unit and norbornadiene, deactivation of the excited state by

Tunable full-color dual-state (solution and solid) emission of push–pull molecules containing the 1-pyrindane moiety

• Anastasia I. Ershova,
• Sergey V. Fedoseev,
• Konstantin V. Lipin,
• Mikhail Yu. Ievlev,
• Oleg E. Nasakin and
• Oleg V. Ershov

Beilstein J. Org. Chem. 2024, 20, 3016–3025, doi:10.3762/bjoc.20.251

• , indicating that the more polar singlet excited state (S1) was much better stabilized by polar solvents than the ground state (S0). The highest fluorescence quantum yield of about 87% was observed in toluene. Then, the solvatochromic properties of stilbazole 1i, bearing a stronger electron-donating

• S4, Supporting Information File 1) and the Kawski–Chamma–Viallet plots [59][60] (Figure 4, see Supporting Information File 1 for details) showed good linearity. This also indicated that the excited-state dipole moment of the molecules was much higher than that in the ground state. This phenomenon was

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

• -AcrClO4 as the photocatalyst has been disclosed (Scheme 24) [67]. According to the authors, the irradiation of the photocatalyst (Acr+-Mes) A with a blue LED leads to the excited state (Acr·-Mes·+) B. The aliphatic carboxylic acid 66 is converted by deprotonation to the corresponding carboxylate, which is

• excited state [*IrIII(ppy)3] is likely to initiate a plausible catalytic cycle. Then TBHP is reduced by [*IrIII(ppy)3] through SET, which results in the generation of the tert-butoxy radical. Subsequently, the tert-butoxy radical abstracts a hydrogen atom from substrate 68 to give radical A

• –peroxidation of alkenes 155 with TBHP and aldehydes 156 through visible-light photocatalysis was developed using fac-Ir(ppy)3 as the photoredox catalyst (Scheme 49) [113]. Under visible light irradiation, the excited state Ir(III)* is generated, and the single electron transfer of Ir(III)* with TBHP results in

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• state, eosin Y*. This excited state further undergoes oxidation via a single-electron-transfer (SET) reaction with Ar2IBF4 26, producing eosin Y+ and a phenyl radical 30 (Scheme 10). The radical intermediate 30 selectively binds to the C2 position of either quinoline or pyridine N-oxide, forming

• mechanism by adding 2 equivalents of TEMPO to the reaction mixture. The absence of the desired product indicated the involvement of a radical pathway in the process. The proposed reaction mechanism begins with the activation of eosin Y by visible light from 5 W blue LEDs, transitioning it to its excited

Investigation of a bimetallic terbium(III)/copper(II) chemosensor for the detection of aqueous hydrogen sulfide

• Parvathy Mini,
• Michael R. Grace,
• Genevieve H. Dennison and
• Kellie L. Tuck

Beilstein J. Org. Chem. 2024, 20, 2818–2826, doi:10.3762/bjoc.20.237

• exhibited high luminescence (with a quantum yield of 68%) and displayed the characteristic trivalent terbium emission bands with emission peaks at 491 nm, 545 nm, 583 nm, and 621 nm, corresponding to transitions from the 5D4 excited state to the 7F6, 7F5, 7F4, and 7F3 ground states, respectively (Figure 2

Photoluminescence color-tuning with polymer-dispersed fluorescent films containing two fluorinated diphenylacetylene-type fluorophores

• Kazuki Kobayashi,
• Shigeyuki Yamada,
• Motohiro Yasui and
• Tsutomu Konno

Beilstein J. Org. Chem. 2024, 20, 2682–2690, doi:10.3762/bjoc.20.225

• diphenylacetylene structure as the π-conjugated core. As a part of our research projects, we have begun to explore diphenylacetylene-based luminescent molecules despite diphenylacetylene not exhibiting fluorescence at room temperature because it undergoes a πσ* excited state that rapidly forms a trans-bend

• structure (Figure 1a) [14][15][16]. Our extensive efforts have revealed that introducing electron-donating alkoxy and electron-withdrawing cyano groups at both ends of the diphenylacetylene scaffold slows the internal conversion to the πσ* excited state. Further incorporating four fluoro substituents in the

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

• excited state, Mes-Acr+*. This excited state then reductively interacts with the sulfinate anion to produce a CF3 radical. The CF3 radical subsequently attacks the target substrate, forming an intermediate radical, which undergoes further oxidation to yield the desired product (Scheme 47a). The Wu group

Photoredox-catalyzed intramolecular nucleophilic amidation of alkenes with β-lactams

• Valentina Giraldi,
• Giandomenico Magagnano,
• Daria Giacomini,
• Pier Giorgio Cozzi and
• Andrea Gualandi

Beilstein J. Org. Chem. 2024, 20, 2461–2468, doi:10.3762/bjoc.20.210

• photocatalysts (PC) that act as oxidants in the excited state [27]. The direct functionalization of amides with alkenes has been a relatively underexplored area in research, as evidenced by the limited number of examples reported in the literature. An interesting observation was made by the Nicewicz group during

• , enhances charge transfer by stabilizing the mesityl moiety. Conversely, the introduction of tert-butyl groups increases the life time of the excited state [52][53][54][55][56]. As a consequence, the PC IV is a strong oxidant in the excited state and displays unique oxidizing properties (E1/2[*PC+/PC

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

Generation of alkyl and acyl radicals by visible-light photoredox catalysis: direct activation of C–O bonds in organic transformations

• Mithu Roy,
• Bitan Sardar,
• Itu Mallick and
• Dipankar Srimani

Beilstein J. Org. Chem. 2024, 20, 1348–1375, doi:10.3762/bjoc.20.119

• . Appropriate selection of the phosphine reagent was the key to success in the process. Due to the lower oxidation potential, electron-rich PMe2Ph preferentially transferred a single electron to the excited state of the photocatalyst rather than the alkene, which was essential for obtaining the desired product

• iridium photocatalyst [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 leads to excited-state *[Ir(III)], Ered (*[Ir(III)]/[Ir(II)]) = +1.21 V, possessing sufficient energy to oxidize PPh3, forming the triphenylphosphine radical cation. Subsequently, benzoic acid undergoes deprotonation facilitated by a base, producing

• excited-state photocatalyst oxidizes the cesium alkyl oxalate via SET, followed by elimination of two carbon dioxide molecules, generating a tertiary alkyl radical that easily combines with an electron-deficient alkene, providing the product. This protocol was well compatible with a wide range of acceptor

Mechanistic investigations of polyaza[7]helicene in photoredox and energy transfer catalysis

• Johannes Rocker,
• Till J. B. Zähringer,
• Matthias Schmitz,
• Till Opatz and
• Christoph Kerzig

Beilstein J. Org. Chem. 2024, 20, 1236–1245, doi:10.3762/bjoc.20.106

• catalyst in the sulfonylation/arylation of styrenes and as a triplet sensitizer in energy transfer catalysis. The singlet lifetime is sufficiently long to exploit the exceptional excited state reduction potential for the activation of 4-cyanopyridine. Photoinduced electron transfer generating the radical

• ][13][14][15]. Most of the established organic catalysts (acridinium salts [16][17][18][19], cyanoarenes [8][20][21][22], quinones [23][24], etc.) [10][25] are cationic or electron-deficient and tend to act as excited state oxidants in a reductive quenching cycle. Only recently, more reducing catalyst

• classes have been investigated, including second-generation cyanoarenes [8], arylamines [26], phenothiazines, phenazines and phenoxazines [9][27][28], which can act as excited state reductants comparable to precious metal-based photoredox catalysts. Singlet-excited organic chromophores often have short

Novel route to enhance the thermo-optical performance of bicyclic diene photoswitches for solar thermal batteries

• Akanksha Ashok Sangolkar,
• Rama Krishna Kadiyam and
• Ravinder Pawar

Beilstein J. Org. Chem. 2024, 20, 1053–1068, doi:10.3762/bjoc.20.93

• singlet vertical electronic excited state energy values computed with the TD-M062X/6-311++G** utilizing Gaussian 16. The data was extracted by considering the half width of 0.33 at the half height of the optical spectrum. The calculated spectral data including the absorption onset (λonset), the first

Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• state thereof, denoted with an asterisk, possessing a reduction potential of 2.0 V versus SCE (saturated calomel electrode). Subsequently, this excited state undergoes quenching through photoinduced electron transfer (PET) with styrene 5. The resulting vinyl radical cation exhibits electrophilicity at

• is worthy of being called anti-Markovnikov hydrochlorination was reported by Nicewicz in 2014 [90]. The inversion of regioselectivity is best understood by examination of the proposed catalytic cycle (Figure 8). First, electronic excitation of photoredox catalyst 149 at 450 nm results in an excited

Synthesis and characterization of water-soluble C₆₀–peptide conjugates

• Yue Ma,
• Lorenzo Persi and
• Yoko Yamakoshi

Beilstein J. Org. Chem. 2024, 20, 777–786, doi:10.3762/bjoc.20.71

• photodynamic therapy photosensitizers (PDT PSs) [41] and magnetic resonance imaging contrast agents (MRI CAs) [42], which are the most relevant topics in fullerene biological studies. Aggregated fullerenes in the micelle structure may cause self-quenching of the excited state of PS fullerenes or may inhibit

SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

• Julien Borrel and
• Jerome Waser

Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64

• studies [45] a plausible photocatalytic cycle could be proposed (Scheme 5). Upon light irradiation, single-electron reduction of Ts-ABZ (3) (E1/2red = −0.62 V vs SCE) [45] by the excited state photocatalyst (E1/2 [RuIII/RuII*] = −0.86 V vs SCE) [53] can occur to form an azide radical, which upon addition

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• (3.15 to 2.06 × 105 s−1) [34] when employing catalytic IrIII excited state reductants with moderate reducing potentials (E1/2red[IrIV/*IrIII] ≈ −1.13 V vs Fc0/Fc+ in MeCN) [35]. This suggests that in the absence of a sufficiently strong driving force, BET and fragmentation compete to influence the

• ], have been employed as suitable photocatalysts (Scheme 4B). Under visible light irradiation the photocatalyst (PC) is excited into its corresponding excited state (*PC), where it can be reduced by a suitable electron donor such as DIPEA or Hantzsch ester to generate the reduced form of the photocatalyst

• a reductive quenching mechanism. However, since the overall transformation is redox-neutral, no stoichiometric reductant was employed. Instead, fluorescence-quenching studies suggested that the reductive quenching of the iridium excited state (*IrIII) was taking place "off-cycle" via oxidation of

Photochromic derivatives of indigo: historical overview of development, challenges and applications

• Gökhan Kaplan,
• Zeynel Seferoğlu and
• Daria V. Berdnikova

Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23

• benzene (Figure 3). This indicates that in addition to structure I, which is traditionally used to depict indigo, intraionic resonance structures II and III with single C–O bonds and double C=N bonds make a pronounced contribution in the ground state of indigo (Figure 3) [13][14]. In the excited state

• hypsochromic shifts of the absorption maxima [24]. These effects can be easily explained considering the direction of the charge transfer in the H-chromophore of indigo upon excitation. Thus, in the excited state, the electron density shifts from the N towards the O atom (Figure 4). Therefore, an increase in

• interest and, therefore, has been investigated comprehensively. To understand the photochemical and photophysical properties of indigo, a great number of theoretical and experimental studies [25][26][27][28][29][30][31][32][33][34][35] have been performed so far, which allowed to characterize excited state

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

• of 63 in toluene revealed that the lowest singlet excited state (S1) decays mono-exponentially to the ground state (S0) within approximately 1 ps, suggesting the existence of an accessible CI between S1 and S0. In the S1 minimum conformation of 63, the PCBD moiety adopted a planar orientation

• room-temperature solution (dichloromethane) and as a frozen matrix at 77 K [123]. This is in contrast with the typical homoleptic phenanthroline-based CuI complexes renowned for their emissions from a triplet metal-to-ligand charge transfer excited state. The absence of luminescence may be attributed

• the plausible energy transfer from the local charge-separated (CS) state of the push–pull chromophore (namely N,N-diethylanilino (DEA)•+–TCBD•−) to the singlet excited state of C60 (1C60*). In transient absorption spectral measurements conducted via the femtosecond laser-flash photolysis of compound