Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

• Henrik Hupatz,
• Marius Gaedke,
• Hendrik V. Schröder,
• Julia Beerhues,
• Arto Valkonen,
• Fabian Klautzsch,
• Sebastian Müller,
• Felix Witte,
• Kari Rissanen,
• Biprajit Sarkar and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2020, 16, 2576–2588, doi:10.3762/bjoc.16.209

• NDI monomer between 300 and 380 nm (Figure 4a–c, black) [59]. A weak charge-transfer band at ≈450 nm is observed for the free macrocycle NDIC7 (Figure 4a, black), which is most likely caused by an intramolecularly folded naphthalene–NDI complex in solution, similar to the crystal structure. In

• contrast, no charge-transfer band is present, neither for NDIRot nor for NDIC8, ruling out the formation of similar charge-transfer complexes in NDIC8 or in the corresponding rotaxane. After one-electron reduction (NDI → NDI•−), a complex absorption band pattern emerges in the visible region of all three

• intramolecular folding which was observed in the solid-state structure and is likely also present in solution, as indicated by a charge-transfer band. Nevertheless, it might be applicable for redox-controlled metal-sensing [60][61][62]. On the contrary, NDIC8 forms pseudo[2]rotaxanes and facilitates the

Conformational preferences of fluorine-containing agrochemicals and their implications for lipophilicity prediction

• Daniela Rodrigues Silva,
• Joyce K. Daré and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2020, 16, 2469–2476, doi:10.3762/bjoc.16.200

• conformer Igg is the most stabilized by the ΔENL term, which can be attributed to the stabilizing interactions featured in the gauche effect [14][20], due to the gauche arrangement along the two F–C–C–O pathways. The charge transfer from the filled σCH orbital to the empty σ*CF or σ*CO orbitals amounts to

• 4.6/4.5 and 3.3 kcal mol−1, respectively, which are more stabilizing than the corresponding σCF/CO → σ*CO/CF and nF/O → σ*CO/CF in the anti-orientation (Table 1). Note that the nF → σ*CO charge transfer is slightly more stabilizing than the σCF → σ*CO, which is in agreement with the findings of

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

• ][33]. When an alkylating agent containing an aryl ring 40 (e.g., phenacyl/benzyl bromides) is used, the enamine intermediate 41 forms a coloured electron-donor acceptor (EDA) complex that can absorb visible light via an intermolecular charge-transfer state (EDA route) [14][34]. Mechanistic

• energy charge transfer state that can be photoexcited to generate singlet intermediate 89*. Subsequent enantioselective photocycloaddition with 88 via diradical 90 gives iminium ion intermediate 91, which after hydrolysis affords the desired cyclobutane products 92 in excellent yields and good

Styryl-based new organic chromophores bearing free amino and azomethine groups: synthesis, photophysical, NLO, and thermal properties

• Anka Utama Putra,
• Deniz Çakmaz,
• Nurgül Seferoğlu,
• Alberto Barsella and
• Zeynel Seferoğlu

Beilstein J. Org. Chem. 2020, 16, 2282–2296, doi:10.3762/bjoc.16.189

• tune intramolecular charge transfer (ICT) intensity and it can increase NLO properties [11][12][13][14]. Some ions such as proton (H+) and hydroxide (OH−), in aqueous environments, play significant roles in industrial, biological, and environmental processes [15][16][17]. Their presence in aqueous

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• , since its first successful synthesis, a variety of functionalized sumanenes as well as heterosumanenes have been developed because of their unique physiochemical properties. For example, bowl-to-bowl inversion, bowl depth, facial selectivity, crystal packing, metal complexes, intermolecular charge

• transfer systems, cation–π complexation, electron conductivity, optical properties and so on. Keeping the importance of this beautiful scaffold in mind, we compiled all the synthetic routes available for the construction of sumanene and its heteroatom derivatives including Mehta’s first unsuccessful effort

Naphthalene diimide–amino acid conjugates as novel fluorimetric and CD probes for differentiation between ds-DNA and ds-RNA

• Annike Weißenstein,
• Myroslav O. Vysotsky,
• Ivo Piantanida and
• Frank Würthner

Beilstein J. Org. Chem. 2020, 16, 2032–2045, doi:10.3762/bjoc.16.170

• colourless and non-fluorescent core-unsubstituted NDI with a new charge transfer band with an absorption maximum in the visible spectral range and a high fluorescence quantum yield (up to 58%) [23][25]. Further, the 2-amino substituent offers the possibility to connect various amino acid side chains, thus

• molecular ground-state electrical dipole (µ = 7.04 D), which is an evidence for an intramolecular charge transfer (CT) character of the chromophore [34]. The predicted UV–vis spectra by TD-DFT are in excellent agreement with the experimental one (Figure 3, Table 1, the vibrational coupling is neglected

• stronger quenching for GC-DNA and the weaker for AT(U)-polynucleotides (Figure 5a and b). Because guanine is the most electron-rich nucleobase, this behaviour points at a fluorescence quenching mechanism by charge transfer from the electron-rich purine bases to the electron-poor NDI molecular probes

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

• an oxidative ortho-C–H addition step via a metal-to-ligand charge transfer process, delivering the Rh(III) hydride species. Following borylation of the Rh(III) intermediate and subsequent reductive elimination liberate the expected coupling product with concomitant regeneration of the catalytically

Clickable azide-functionalized bromoarylaldehydes – synthesis and photophysical characterization

• Dominik Göbel,
• Marius Friedrich,
• Enno Lork and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2020, 16, 1683–1692, doi:10.3762/bjoc.16.139

• facilitate the ISC process from S1 to Tn and thus increase the spin-orbital coupling [38][39][40][41][42][43][44][45][46][47]. Also, decreasing the singlet–triplet splitting energy (ΔEST) caused by intramolecular charge-transfer (ICT) interactions is an approved method [48][49]. (2) Significant reduction of

Models of necessity

• Timothy Clark and
• Martin G. Hicks

Beilstein J. Org. Chem. 2020, 16, 1649–1661, doi:10.3762/bjoc.16.137

• reactivity. However, it is too unwieldy for everyday communication. Qualitative bonding concepts The basic conundrum remains. If we cannot define atoms within molecules, we cannot define atomic charges or bonds between atoms or interatomic concepts such as charge transfer. It is important to emphasize here

• how well the results fit with the user’s own preferences and prejudices. Take, for instance, the concepts of polarization and charge transfer. Of these two closely related concepts, polarization is real and observable (e.g., through a change in dipole moment), whereas charge transfer is a qualitative

• concept that can neither be defined nor observed uniquely. This is illustrated in Figure 4. Polarization (above) involves a shift of electrons from the gray atom to the cyan one; charge transfer from the gray/cyan molecule to the red atom. The charge shift in the two examples is identical. Simply moving

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

• charge–transfer transitions [95]. These transitions are commonly observed in metal–organic framework (MOF) HPCats, discussed more in Section 2.5. Dye-sensitised semiconductor photocatalysts have organic photosensitiser molecules immobilised to their surface. This strategy is typically used to activate a

• wide-band gap semiconductor towards visible light excitation [95]. The photosensitiser can inject electrons to the semiconductor conduction band via direct HOMO–CB transition (type II excitation) or indirectly by exciting the photosensitiser HOMO–LUMO transition, followed by a LUMO–CB charge transfer

• (HER). The FSO-FS polymer displayed the highest rates of hydrogen evolution (170 μmol⋅h−1), significantly higher than its structural isomer FSO-FSz. The authors studied the charge transfer dynamics of the different polymers through temperature-dependent photoluminescence, photoelectrochemical

An overview on disulfide-catalyzed and -cocatalyzed photoreactions

• Yeersen Patehebieke

Beilstein J. Org. Chem. 2020, 16, 1418–1435, doi:10.3762/bjoc.16.118

• decomposes into ketone or aldehyde products (Scheme 9). However, in the absence of light or oxygen, disulfide could not catalyze the oxidative cleavage of olefins. It was proposed that disulfide and the olefin might be able to form a charge-transfer complex, which may rationalize the unconventional homolysis

Oxime radicals: generation, properties and application in organic synthesis

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Alexander S. Budnikov and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107

• radical mechanism in which the iminoxyl radical is generated from the oxime anion under the action of perfluorobutyl iodide through the formation of an EDA complex (electron donor–acceptor complex, which is also called charge-transfer complex). The perfluorobutyl radical formed at this step served for the

Synthesis and properties of quinazoline-based versatile exciplex-forming compounds

• Rasa Keruckiene,
• Simona Vekteryte,
• Ervinas Urbonas,
• Matas Guzauskas,
• Eigirdas Skuodis,
• Dmytro Volyniuk and
• Juozas V. Grazulevicius

Beilstein J. Org. Chem. 2020, 16, 1142–1153, doi:10.3762/bjoc.16.101

• to a quasi-orthogonal geometry of the donor part on the acceptor core, and the charge-transfer (CT) character [16]. On the other hand, not adapting the vertical dihedral angle enabled a slight HOMO and LUMO overlap in the geometry of compound 1. This resulted in a higher oscillator strength of 0.0109

• moieties, respectively [19]. Additionally, a weak absorption band (shoulder) at ca. 348 nm was detected for compound 2, evidencing an intramolecular charge transfer (ICT) between the phenothiazine and quinazoline units. The energy band gap values determined from the edges of the experimental UV spectra of

• compounds, the transition took place between orbitals delocalized over both donor fragments and the quinazoline moiety indicating a charge transfer in vacuum. Considering the experimental data, it could be presumed that this 1CT state is very sensitive and easily quenched in polar solvents as it competes

Synthesis of novel multifunctional carbazole-based molecules and their thermal, electrochemical and optical properties

• Nuray Altinolcek,
• Ahmet Battal,
• Mustafa Tavasli,
• William J. Peveler,
• Holly A. Yu and
• Peter J. Skabara

Beilstein J. Org. Chem. 2020, 16, 1066–1074, doi:10.3762/bjoc.16.93

• distinctive absorption bands: high and mid energy bands due to locally excited (LE) transitions and low energy bands due to intramolecular charge transfer (ICT) transitions. In dichloromethane solutions compounds 7a and 7b gave emission maxima at 561 nm and 482 nm with quantum efficiencies of 5.4% and 97.4

• Fluorescence and Absorbance Spectrometer. Each compound (7a/7b) displayed three distinctive absorption bands in the UV–vis spectra: high energy bands and mid energy bands were assigned to π–π* and n–π* transitions, whereas the low energy bands were assigned to an intramolecular charge transfer (ICT) transition

• dependent on the excitation wavelength chosen and the solvent used. It is believed that the dual emission was due to mixed locally excited (LE) and intramolecular charge transfer (ICT) states and the single emission was due to the ICT state. Photoluminescence (PL) spectra of compounds 7a and 7b in different

Aryl-substituted acridanes as hosts for TADF-based OLEDs

• Naveen Masimukku,
• Dalius Gudeika,
• Oleksandr Bezvikonnyi,
• Ihor Syvorotka,
• Rasa Keruckiene,
• Dmytro Volyniuk and
• Juozas V. Grazulevicius

Beilstein J. Org. Chem. 2020, 16, 989–1000, doi:10.3762/bjoc.16.88

• to polarity and aggregation effects. Despite these observations, emission of compounds 3–6 can mainly be assigned to π–π* transitions of local excited states. However, a slight contribution of charge transfer (CT) can be also recognized in the emission of the studied compounds 3–6 (Figure 3a). The

Recent applications of porphyrins as photocatalysts in organic synthesis: batch and continuous flow approaches

• Rodrigo Costa e Silva,
• Luely Oliveira da Silva,
• Aloisio de Andrade Bartolomeu,
• Timothy John Brocksom and
• Kleber Thiago de Oliveira

Beilstein J. Org. Chem. 2020, 16, 917–955, doi:10.3762/bjoc.16.83

• chemical transformations come from this process, whose crucial step involves the formation of a charge-transfer complex between singlet oxygen and the amine. Subsequently, hydrogen-atom abstraction leads to the radical intermediate, which can undergo SET with a hydroperoxyl radical to afforded an iminium

Cation-induced ring-opening and oxidation reaction of photoreluctant spirooxazine–quinolizinium conjugates

• Phil M. Pithan,
• Sören Steup and
• Heiko Ihmels

Beilstein J. Org. Chem. 2020, 16, 904–916, doi:10.3762/bjoc.16.82

• extended π system or an intramolecular charge transfer (ICT). This property may allow to use visible light with longer wavelength to induce the ring-opening reaction, which would be favorable, e.g., for biological applications. The stilbene etheno bridge, however, may also lead to an intricate photochromic

Bipyrrole boomerangs via Pd-mediated tandem cyclization–oxygenation. Controlling reaction selectivity and electronic properties

• Liliia Moshniaha,
• Marika Żyła-Karwowska,
• Joanna Cybińska,
• Piotr J. Chmielewski,
• Ludovic Favereau and
• Marcin Stępień

Beilstein J. Org. Chem. 2020, 16, 895–903, doi:10.3762/bjoc.16.81

• up to 67%, while their bandgaps and chiroptical responses could be tuned by twisting the bipyrrole chromophore. The solvatochromism and apparent superradiance of these chromophores indicated a potential involvement of solvent-induced symmetry-breaking charge transfer in the excited state [34]. Here

Aldehydes as powerful initiators for photochemical transformations

• Maria A. Theodoropoulou,
• Nikolaos F. Nikitas and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2020, 16, 833–857, doi:10.3762/bjoc.16.76

• extinction coefficients and charge transfer states as well as relatively long-lived triplet states in solution, making them suitable as photoinitiators [36][37]. The irradiation and excitation of DEABP (27) to the singlet state is followed by intersystem crossing to the triplet state 29, which then leads to

One-pot synthesis of dicyclopenta-fused peropyrene via a fourfold alkyne annulation

• Ji Ma,
• Yubin Fu,
• Junzhi Liu and
• Xinliang Feng

Beilstein J. Org. Chem. 2020, 16, 791–797, doi:10.3762/bjoc.16.72

• -membered ring B. The large difference between the LUMO and HOMO leads to an intramolecular charge transfer, resulting in broad absorption bands in the UV–vis spectrum (Figure 3a) [36]. In addition, the LUMO energy of 1 (−2.98 eV) is significantly lower than that of 6 (−2.38 eV), which is responsible for

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

• Kaj M. van Vliet,
• Nicole S. van Leeuwen,
• Albert M. Brouwer and
• Bas de Bruin

Beilstein J. Org. Chem. 2020, 16, 398–408, doi:10.3762/bjoc.16.38

• could also play a role. For every lactone product that is formed, HCl is generated and in the case of fac-[Ir(ppy)3], the acid could potentially cause protodemetalation. This protodemetalation could be even more pronounced in the excited state (which is after all a metal-to-ligand charge-transfer state

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

• Rafia Siddiqui and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26

• seen in Figure 8, the mechanism of the reaction commences with the deprotonation of the biphenyl carboxylic acid 36, followed by the reaction of 38 with dimethyl dicarbonate (DMDC) to generate compound 39. On the other hand, the photocatalyst is excited by metal–ligand charge transfer, which produces

Synthesis, liquid crystalline behaviour and structure–property relationships of 1,3-bis(5-substituted-1,3,4-oxadiazol-2-yl)benzenes

• Afef Mabrouki,
• Malek Fouzai,
• Armand Soldera,
• Abdelkader Kriaa and
• Ahmed Hedhli

Beilstein J. Org. Chem. 2020, 16, 149–158, doi:10.3762/bjoc.16.17

• electron D–A concept may be regarded as Lewis base–Lewis acid type or charge-transfer. Based upon the above considerations, we could attribute the close proximity of fluorinated chains in conformation B to a throw space electron D–A intramolecular interaction between the perfluoroalkyl chains (electron

Reversible photoswitching of the DNA-binding properties of styrylquinolizinium derivatives through photochromic [2 + 2] cycloaddition and cycloreversion

• Sarah Kölsch,
• Heiko Ihmels,
• Jochen Mattay,
• Norbert Sewald and
• Brian O. Patrick

Beilstein J. Org. Chem. 2020, 16, 111–124, doi:10.3762/bjoc.16.13

• , the strong donor–acceptor system in 3a led to an intramolecular charge-transfer (ICT) state that did not lead to a subsequent photoreaction [77]. In contrast, the absorption bands of the substrates 3b–d decreased relatively fast upon irradiation, but the maxima did not disappear completely (Figure 5B

Synthesis and optoelectronic properties of benzoquinone-based donor–acceptor compounds

• Daniel R. Sutherland,
• Nidhi Sharma,
• Georgina M. Rosair,
• Ifor D. W. Samuel,
• Ai-Lan Lee and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2019, 15, 2914–2921, doi:10.3762/bjoc.15.285

• benzoquinone (BQ)-based charge-transfer (CT) derivatives in good yields. The optoelectronic properties of these compounds were explored both theoretically and experimentally and correlations to their structures were identified as a function of the nature and position of the donor group (meta and para) attached

• arylboronic acids are readily accessible, we envisaged that our Pd-catalyzed direct C–H functionalization method would be ideal for attempting a facile and direct route to a series of novel substituted benzoquinone-based charge-transfer derivatives, with the aim of exploring their electroluminescent (EL

• is difficult to realize highly efficient TADF emitters, which is especially the case for red emitters where nonradiative rates are high due to the well-known energy gap law [28]. While anthraquinone-based charge-transfer compounds have recently been shown to exhibit TADF that then translated to their