Fluorescent phosphorus dendrimers excited by two photons: synthesis, two-photon absorption properties and biological uses

• Anne-Marie Caminade,
• Artem Zibarov,
• Eduardo Cueto Diaz,
• Aurélien Hameau,
• Maxime Klausen,
• Kathleen Moineau-Chane Ching,
• Jean-Pierre Majoral,
• Jean-Baptiste Verlhac,
• Olivier Mongin and
• Mireille Blanchard-Desce

Beilstein J. Org. Chem. 2019, 15, 2287–2303, doi:10.3762/bjoc.15.221

• intersystem conversion towards a triplet state (T1), from which there will be emission of phosphorescence, having generally a lifetime longer than that of fluorescence. This classical one-photon excited fluorescence has led to the design of numerous types of chemical entities since the XIX century. For

Synthesis and properties of sulfur-functionalized triarylmethylium, acridinium and triangulenium dyes

• Marco Santella,
• Eduardo Della Pia,
• Jakob Kryger Sørensen and
• Bo W. Laursen

Beilstein J. Org. Chem. 2019, 15, 2133–2141, doi:10.3762/bjoc.15.210

• fluorescence lifetime (τfl) [12][13] are key photophysical properties to consider and optimize for any given application. We have for quite some time been interested in the synthesis, properties and applications of dyes from the triangulenium family (Figure 1) [14][15]. The triangulenium dyes can be divided

• fluorescence lifetime has been a key point of interest since it enables time-gated detection for suppression of autofluorescence [25][26] and provides attractive advantages in fluorescence polarization assays [13][27][28]. A common characteristic feature of triangulenium dye synthesis is the use of methoxy

Naphthalene diimides with improved solubility for visible light photoredox catalysis

• Barbara Reiß and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2019, 15, 2043–2051, doi:10.3762/bjoc.15.201

• catalysis is mainly [Ru(bpy)3]2+ [21], due to its strong MLCT (metal-to-ligand charge transfer) absorption, the excellent yield of its triplet state and the long lifetime, the versatile redox behavior (Ru3+ vs Ru+) in quenching processes and the chemical and photochemical robustness. Despite their positive

Synthesis, enantioseparation and photophysical properties of planar-chiral pillar[5]arene derivatives bearing fluorophore fragments

• Guojuan Li,
• Chunying Fan,
• Guo Cheng,
• Wanhua Wu and
• Cheng Yang

Beilstein J. Org. Chem. 2019, 15, 1601–1611, doi:10.3762/bjoc.15.164

• quantum yield was only slightly decreased. This should be mainly due to the steric hindrance of the 9- and 10-phenyl groups, which inhibited the π–π stacking of the anthracene core in DPA. The fluorescent lifetimes of P5A-Py and P5A-DPA were compared with Py-6 and DPA-6. As shown in Figure 2, the lifetime

• of P5A-Py is 3.4 ns which is shorter than that of Py-6 (4.4 ns), demonstrating that grafting two Py units in close proximity in one host, opened a new route for nonradiative decay. This phenomenon further verified the occurrence of π–π stacking of the Py fragments in P5A-Py. The lifetime of P5A-DPA

• ) apparatus. UV–vis spectra were obtained on a JASCO v-650 spectrometer. Fluorescence spectra and fluorescence lifetime decay measurements were recorded on a HORIBA FluoroMax–4 (TCSPC) spectrofluorimeter. Circular dichroism spectra were measured on a JASCO J-1500 spectrometer using a quartz cuvette of 1 cm

Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings

• Manuel Pedrón,
• Laura Legnani,
• Maria-Assunta Chiacchio,
• Pierluigi Caramella,
• Tomás Tejero and
• Pedro Merino

Beilstein J. Org. Chem. 2019, 15, 1552–1562, doi:10.3762/bjoc.15.158

• bond and formation of the O–H bond but the resulting iminium ion was stable enough to be considered a real intermediate according to IUPAC definition of 1994, which is: “A molecular entity with a lifetime appreciably longer than a molecular vibration – corresponding to a local potential energy minimum

• some chemical behavior. Indeed, further theoretical studies on MD simulations would be needed to elucidate the lifetime of the transient carbocation [34][35]. These results demonstrate the one-step-two-stage character [42] of the ruthenium oxidations of alkanes in which H transfer and O–C bond

Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response

• Yu-Ying Wang,
• Yong Kong,
• Zhe Zheng,
• Wen-Chao Geng,
• Zi-Yi Zhao,
• Hongwei Sun and
• Dong-Sheng Guo

Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139

• a PET pathway. The fluorescence lifetime of AlPcS4 remains unaltered after addition of GC5A, indicating the absence of dynamic quenching of the residual uncomplexed AlPcS4 and therefore confirming the formation of a statically quenched complex. UV–vis titration further verified the formation of a

Unexpected polymorphism during a catalyzed mechanochemical Knoevenagel condensation

• Sebastian Haferkamp,
• Andrea Paul,
• Adam A. L. Michalchuk and
• Franziska Emmerling

Beilstein J. Org. Chem. 2019, 15, 1141–1148, doi:10.3762/bjoc.15.110

• concentrations of catalyst. To better observe this transformation pathway, the reaction (2 µL catalyst) was repeated at 30 Hz in order to extend the lifetime of m3a. The in situ XRPD pattern and Raman spectra are shown in Figure 4b and d, respectively. Decreasing the milling frequency has a number of notable

• effects. First, the lifetime of the initial molten/liquid phase was nearly doubled, suggesting that mechanical treatment has an important effect on this largely solution-phase reaction. This may be a result of heating, mechanical activation of the fluid-phase molecules or differences in energy for

• nucleation. While further work is required in this area, it is clear that mechanical treatment can have notable influence on ‘solution-phase’ chemistry. Second, the lifetime of the intermediate phase was extended. This allowed us to collect higher resolution XRPD data by extracting a sample from the milling

Precious metal-free molecular machines for solar thermal energy storage

• Meglena I. Kandinska,
• Snejana M. Kitova,
• Vladimira S. Videva,
• Stanimir S. Stoyanov,
• Stanislava B. Yordanova,
• Stanislav B. Baluschev,
• Silvia E. Angelova and
• Aleksey A. Vasilev

Beilstein J. Org. Chem. 2019, 15, 1096–1106, doi:10.3762/bjoc.15.106

• concentration (1 × 10−4 M) for all dyes. The kinetic data were found to fit well to a single exponential function (Equation 1), giving a rate constant (k) corresponding to a lifetime (1/k) [18]: where A0 and A∞, are the initial and final absorptions, A is the absorption at 500 nm at a time t after termination

• dyes are summarized in Table 2. Generally, the addition of Ba2+ ions was found to increase substantially the lifetime of the cis isomers. Under the abovementioned conditions the cis-4b–Ba2+ complex was detected to be most stable, while dye 4d formed stable cis-4d–Ba2+ complex only at a higher

• ) → LUMO (lowest unoccupied molecular orbital) transitions. The simulated spectra with spectral lifetime broadening (Gaussian function) with a full width at half-maximum (FWHM) of 0.15 eV and a height proportional to the oscillator strength for each transition spectrum for dye 4b and its Ba2+ complex

Photochemical generation of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical from caged nitroxides by near-infrared two-photon irradiation and its cytocidal effect on lung cancer cells

• Ayato Yamada,
• Manabu Abe,
• Yoshinobu Nishimura,
• Shoji Ishizaka,
• Masashi Namba,
• Taku Nakashima,
• Kiyofumi Shimoji and
• Noboru Hattori

Beilstein J. Org. Chem. 2019, 15, 863–873, doi:10.3762/bjoc.15.84

• reactivity of the singlet excited states of 2a and 2b. Time-correlated single photon counting (TCSPC) measurement was performed at 298 K in DMSO to estimate the fluorescence lifetime (τ) of 2 and 5 (Table 1). Single-exponential decay curves were observed for 5a and 5b, respectively (Supporting Information

• irradiation (Figure 2h). In DMSO, the quantum yield for the formation of TEMPO increased significantly to 13.1% (from 2a) and 12.8% (from 2b) at ≈1% conversion of 2 under atmospheric conditions (Figure 1). The notable effect of the solvent on the TEMPO generation may be due to the increase in the lifetime of

Catalysis of linear alkene metathesis by Grubbs-type ruthenium alkylidene complexes containing hemilabile α,α-diphenyl-(monosubstituted-pyridin-2-yl)methanolato ligands

• Tegene T. Tole,
• Johan H. L. Jordaan and
• Hermanus C. M. Vosloo

Beilstein J. Org. Chem. 2019, 15, 194–209, doi:10.3762/bjoc.15.19

• Grubbs 2-type (5) metal carbenes with pyridinyl alcoholato ligands for the 1-octene metathesis reaction (Figure 3) [10][11][12][13][14]. The incorporation of pyridinyl-alcoholato ligands in the Grubbs-type precatalysts has shown an increase in the thermal stability, activity and lifetime of the

N-Arylphenothiazines as strong donors for photoredox catalysis – pushing the frontiers of nucleophilic addition of alcohols to alkenes

• Fabienne Speck,
• David Rombach and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2019, 15, 52–59, doi:10.3762/bjoc.15.5

• fast access to a wide variety of catalysts. Recently it was shown that the radical cation of the photoredox catalyst can play a key role in photoinduced oxidation chemistry [16]. This is rather unusual due to the usually short lifetime of radical cations in solution attributed to their low-lying

Degenerative xanthate transfer to olefins under visible-light photocatalysis

• Atsushi Kaga,
• Xiangyang Wu,
• Joel Yi Jie Lim,
• Hirohito Hayashi,
• Yunpeng Lu,
• Edwin K. L. Yeow and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2018, 14, 3047–3058, doi:10.3762/bjoc.14.283

• agreement with the lower process efficiency (Table 1, entry 1) observed in the reaction with fac-Ir(ppy)3 (6) that possesses a lower triplet energy (ET = 55.2 kcal/mol [50]). The optimal photocatalyst 8 [47] has a longer excited state lifetime than 7 does [46], suggesting that the lifetime of the excited

• = 1.25 × 107 M−1s−1 (see Supporting Information File 1). On the other hand, the addition of 1-octene (2a, 40 mM), in place of xanthate 1a, resulted in only a small PL quenching of photocatalyst 8 (<8%, Figure 1B). The time-resolved PL lifetime decay profiles of photocatalyst 8 (25 μM solution in degassed

• DMSO, 410 nm pulse excitation and monitoring emission at 480 nm) were recorded in the absence of a quencher, and in the presence of xanthate 1a and 1-octene (2a, 40 mM, Figure 1C). The lifetime profiles were described using a mono-exponential decay function with a lifetime of 1.40 μs in the absence of

Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region

• Aude-Héloise Bonardi,
• Frédéric Dumur,
• Guillaume Noirbent,
• Jacques Lalevée and
• Didier Gigmes

Beilstein J. Org. Chem. 2018, 14, 3025–3046, doi:10.3762/bjoc.14.282

• react, the PC must have a lifetime of its triplet excited state that is long enough. The bond dissociation energy of the Si–H of (TMS)3SiH has been calculated: 79.8 kcal/mol (methods of calculation optimized at the B3LYP/6-31G* level as referred in [32]). Polymerization performances of photoredox

• cycles can be observed with Ru(bpy)3. Other ruthenium complexes which can be used into photocatalytical cycles have been described in the literature and more particularly with other type of ligands. Modification of the ligands has an influence on the redox potentials and the lifetime of the excited

• photopolymerization initiation as shown in [53] (see Part 3). For this purpose, the Ir complex was more interesting than the Ru one because of the longer excited state lifetime, lower oxidation potential leading to higher interaction rate constants with additives used for ring-opening photopolymerization (e.g

Photocatalyic Appel reaction enabled by copper-based complexes in continuous flow

• Clémentine Minozzi,
• Jean-Christophe Grenier-Petel,
• Shawn Parisien-Collette and
• Shawn K. Collins

Beilstein J. Org. Chem. 2018, 14, 2730–2736, doi:10.3762/bjoc.14.251

• of −1.93 V vs. SCE, much greater than that of Ru(bpy)3+2 (−0.81 V vs SCE), albeit the copper complex has a much shorter excited state lifetime (≈4 ns vs ≈1100 ns for Ru(bpy)3+2). The excited state reduction potential should match favorably with CBr4 (E½ = 0.30 V vs SCE) in DMF [29]. Note that many of

Learning from B₁₂ enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis

• Keishiro Tahara,
• Ling Pan,
• Toshikazu Ono and
• Yoshio Hisaeda

Beilstein J. Org. Chem. 2018, 14, 2553–2567, doi:10.3762/bjoc.14.232

• (II) species and an alkyl radical intermediate A [54]. The prolonged lifetime of the radical intermediate A could be provided by the channel of MOF, enabling conversion to the acetyl-migrated radical B. The radicals A and B may abstract hydrogen radicals to form the reduced product and the acetyl

Synergistic electrodeposition of bilayer films and analysis by Raman spectroscopy

• Saadeldin E. T. Elmasly,
• Luca Guerrini,
• Joseph Cameron,
• Alexander L. Kanibolotsky,
• Neil J. Findlay,
• Karen Faulds and
• Peter J. Skabara

Beilstein J. Org. Chem. 2018, 14, 2186–2189, doi:10.3762/bjoc.14.191

• two layers. Successful PEDOT/PEDTT bilayer formation has been confirmed by Raman spectroscopy. Electrodeposition of the bilayer has advantages over traditional processing methods including avoiding the acidity of PSS which is detrimental to the lifetime of devices containing PEDOT:PSS [18] and the

Applications of organocatalysed visible-light photoredox reactions for medicinal chemistry

• Michael K. Bogdos,
• Emmanuel Pinard and
• John A. Murphy

Beilstein J. Org. Chem. 2018, 14, 2035–2064, doi:10.3762/bjoc.14.179

• process through which energy is transferred between chromophores via non-radiative dipole–dipole coupling. It is generally assumed that the non-radiative processes occur at a much slower rate than radiative processes. As such, the lifetime of S1 (τs1) is roughly equal to the lifetime of fluorescence (τf

• comparable to or larger than the Φf and, more importantly, the rate constant for ISC (kISC) must be similar to the rate constant for fluorescence (kf). The lifetime of the T1 state (τT1) is generally orders of magnitude longer than the timescale of electron transfer (ET), meaning that τT1 does not alter the

Synthesis and photophysical studies of a multivalent photoreactive Ru^II-calix[4]arene complex bearing RGD-containing cyclopentapeptides

• Sofia Kajouj,
• Lionel Marcelis,
• Alice Mattiuzzi,
• Adrien Grassin,
• Damien Dufour,
• Pierre Van Antwerpen,
• Didier Boturyn,
• Eric Defrancq,
• Mathieu Surin,
• Julien De Winter,
• Pascal Gerbaux,
• Ivan Jabin and
• Cécile Moucheron

Beilstein J. Org. Chem. 2018, 14, 1758–1768, doi:10.3762/bjoc.14.150

• luminescence lifetime and determined the quantum yield of luminescence under air and argon atmosphere for conjugate 9 and reference [Ru(TAP)2phen]2+ in water with 5% DMSO in order to avoid any formation of aggregates. The data gathered in Table 1 clearly indicate that the tethering of the [Ru(TAP)2phen]2

• excited state lifetime of conjugate 9 as function of the concentration of guanosine monophosphate (GMP, Figure 4). Stern–Volmer analyses indicate that a dynamic quenching is occurring, with a quenching rate close to the diffusion limit (kQ = 5.6 108 M−1s−1 in intensity and kQ = 5.3 108 M−1s−1 in lifetime

• -SPC) technique with the Edinburgh Instruments LifeSpecII Picosecond Fluorescence Lifetime Spectrometer equipped with a laser diode (λ = 439 nm, pulse = 100 ps). The samples were thermostatted at 20 ± 2 °C with a Haake Model NB22 temperature controller. The data were collected by a multichannel

Natural and redesigned wasp venom peptides with selective antitumoral activity

• Marcelo D. T. Torres,
• Gislaine P. Andrade,
• Roseli H. Sato,
• Cibele N. Pedron,
• Tania M. Manieri,
• Giselle Cerchiaro,
• Anderson O. Ribeiro,
• Cesar de la Fuente-Nunez and
• Vani X. Oliveira Jr.

Beilstein J. Org. Chem. 2018, 14, 1693–1703, doi:10.3762/bjoc.14.144

• , Cambridge, 02139, MA, United States of America 10.3762/bjoc.14.144 Abstract About 1 in 8 U.S. women (≈12%) will develop invasive breast cancer over the course of their lifetime. Surgery, chemotherapy, radiotherapy, and hormone manipulation constitute the major treatment options for breast cancer. Here, we

The phenyl vinyl ether–methanol complex: a model system for quantum chemistry benchmarking

• Dominic Bernhard,
• Fabian Dietrich,
• Mariyam Fatima,
• Cristóbal Pérez,
• Hannes C. Gottschalk,
• Axel Wuttke,
• Ricardo A. Mata,
• Martin A. Suhm,
• Melanie Schnell and
• Markus Gerhards

Beilstein J. Org. Chem. 2018, 14, 1642–1654, doi:10.3762/bjoc.14.140

• temporally overlapping laser pulses, the spectrum contains transitions from the S0 state, the electronically excited (S1, at 3637 cm−1) and also the ionic D0 state (at 3667 cm−1). This could not be avoided, as the lifetime of the excited state, which is estimated to be in the order of 5–7 ns, is shorter than

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

• Cristina Cebrián and
• Matteo Mauro

Beilstein J. Org. Chem. 2018, 14, 1459–1481, doi:10.3762/bjoc.14.124

• ) derivatives undoubtedly play leading roles as electro-active materials in light-emitting devices. Their outstanding photophysical and electrochemical features enabled fabrication of PhOLEDs and LEECs [11] with enhanced device performances in terms of efficiency, operating lifetime and colour purity. In

• shorter exciton lifetime that contributes to reduce detrimental nonradiative processes such as triplet–triplet annihilation (TTA) and triplet–polaron annihilation (TPA). On the other hand, strong σ-donor NHC carbenes ligands could be regarded as the neutral variant of phenylate-like counterparts [28][29

• electroluminescence with remarkable estimated 97% operational lifetime, LT97, over 600 hours at 1000 cd cm−2 and peak EQE of 10.8%. Nonetheless, further improvement of the device efficiency upon variation of host material increased the EQE value up to 21.5% when a dopant concentration of 2 wt % and the ambipolar

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

Two novel blue phosphorescent host materials containing phenothiazine-5,5-dioxide structure derivatives

• Feng-Ming Xie,
• Qingdong Ou,
• Qiang Zhang,
• Jiang-Kun Zhang,
• Guo-Liang Dai,
• Xin Zhao and
• Huai-Xin Wei

Beilstein J. Org. Chem. 2018, 14, 869–874, doi:10.3762/bjoc.14.73

• lifetime. Carbazole groups are widely used in host materials because of their high triplet energy levels and high hole mobility [15]. The Lee group [16] linked carbazolyl groups to diphenyl phosphoramines to design asymmetric (9-phenyl-9H-carbazole-2,5-diyl)bis(diphenylphosphine oxide) (PCPOs) with a

• intermolecular forces of molecules. The high thermal values ensure high thermostability and that the amorphous structure can form homogeneous and stable films by vacuum deposition to improve the lifetime of the PhOLEDs. The photophysics, electrochemical and thermal properties of CEPDO and CBPDO are summarized in

Phosphodiester models for cleavage of nucleic acids

• Satu Mikkola,
• Tuomas Lönnberg and
• Harri Lönnberg

Beilstein J. Org. Chem. 2018, 14, 803–837, doi:10.3762/bjoc.14.68

• intermediate [31]. The lifetime for the dianionic pentacoordinated species obtained by the attack of the hydroxide ion on the phosphorus has been argued to represent an energy minimum between the transition states for the attack of HO− and the departure of EtO− and to have a lifetime of 1 picosecond. With

• leaving groups that are less basic than EtO−, such as 5´-O− of nucleoside, the lifetime expectedly is shorter. If the leaving group is very good, such as an aryl group, a synchronous concerted mechanism (ANDN) may take over the stepwise mechanism (AN + DN). Model compounds and experimental tools Studies

D–A–D-type orange-light emitting thermally activated delayed fluorescence (TADF) materials based on a fluorenone unit: simulation, photoluminescence and electroluminescence studies

• Lin Gan,
• Xianglong Li,
• Xinyi Cai,
• Kunkun Liu,
• Wei Li and
• Shi-Jian Su

Beilstein J. Org. Chem. 2018, 14, 672–681, doi:10.3762/bjoc.14.55

• lifetime of the prompt and delayed components of the time-resolved transient PL decay curves at room temperature, the PLQY of their respective components and rate constant of different kinetic processes were calculated, as shown in Table 4. The rate constants were calculated following Equations 1–4 below