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

• properties, also in terms of electrochemistry. Additionally, the presence of a heavy metal atom induces spin-orbit coupling (SOC) effects to such an extent that intersystem crossing (ISC) processes become thus competitive over other radiationless deactivation pathways owing to relaxation of spin rules. In

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

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

• increase the cost of the final OLEDs. Alternatively, a thermally activated delayed fluorescence (TADF) material is a kind of noble-metal-free fluorescent material able to transform triplet excitons into singlet excitons through reverse intersystem crossing (RISC) to achieve 100% IQEmax in theory [4]. On the

• property according to the energy gap law [16] as vibrational relaxation and intersystem crossing (IC) processes can consume the energy in S1, leading to increased nonradiative deactivation [17], reduced PL quantum yield, and thus reduced singlet exciton utilization. On the contrary, the geometry of 2 is

• [5][7][16]. where kr, knr, kisc, and krisc represent the rate constant of radiative, nonradiative, intersystem crossing and reverse intersystem crossing, respectively; Φ, ΦPF, ΦTADF, τPF and τTADF represent the photoluminescence quantum yield, quantum yield of the prompt component, quantum yield of

Recent advances on organic blue thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs)

• Thanh-Tuân Bui,
• Fabrice Goubard,
• Malika Ibrahim-Ouali,
• Didier Gigmes and
• Frédéric Dumur

Beilstein J. Org. Chem. 2018, 14, 282–308, doi:10.3762/bjoc.14.18

• singlet excited states by reverse intersystem crossing (RISC). By harvesting both singlet and triplet excitons for light emission, OLEDs competing and sometimes overcoming the performance of phosphorescence-based OLEDs could be fabricated, justifying the interest for this new family of materials massively

• , only singlet excitons can be utilized for light emission, limiting the internal quantum efficiency (IQE) of fluorescent OLEDs to 25%. Conversely, phosphorescent materials can both harvest singlet and triplet excitons for emission by intersystem crossing (ISC), enabling to reach a theoretical IQE of 100

• delayed fluorescence (TADF) emitters. As specificity, these materials can thermally repopulate the singlet state from the triplet state by reverse intersystem crossing (RISC), leading to an increase of the luminescence intensity. From the OLEDs viewpoint, TADF emitters behave by harvesting both singlet

Pyrene–nucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies

• Artur Jabłoński,
• Yannic Fritz,
• Hans-Achim Wagenknecht,
• Rafał Czerwieniec,
• Tytus Bernaś,
• Damian Trzybiński,
• Krzysztof Woźniak and
• Konrad Kowalski

Beilstein J. Org. Chem. 2017, 13, 2521–2534, doi:10.3762/bjoc.13.249

• fluorescence intensity and fast decay of fluorescence were rationalized by the presence of low-energy nπ* excited states. In particular, for the lowest excited singlet state 1ππ* efficient intersystem crossing to a triplet state 3nπ* close in energy can be expected according to the El-Sayed rule. Then, this

• pyrene 1ππ* state). Thus, intersystem crossing between these two states can be efficient giving rise to also efficient radiationless depopulation of the emissive singlet state relative to aliphatic analogues, in that quenching 3nπ* states are not present. Interactions with oligonucleotides Compounds 2–5

Cycloheximide congeners produced by Streptomyces sp. SC0581 and photoinduced interconversion between (E)- and (Z)-2,3-dehydroanhydrocycloheximides

• Li Yang,
• Ping Wu,
• Jinghua Xue,
• Huitong Tan,
• Zheng Zhang and
• Xiaoyi Wei

Beilstein J. Org. Chem. 2017, 13, 1039–1049, doi:10.3762/bjoc.13.103

• relaxations via an intersystem crossing (ISC) from the S1 minima 2b and 3b to the T1 maxima 2c and 3c, respectively, are energetically and symmetrically reasonable [14][17] as well as are preferred according to El-Sayed’s rules [18]. Therefore, the isomerization of 2a/3a, after vertical excitation, is

A self-assembled cyclodextrin nanocarrier for photoreactive squaraine

• Ulrike Kauscher and
• Bart Jan Ravoo

Beilstein J. Org. Chem. 2016, 12, 2535–2542, doi:10.3762/bjoc.12.248

• appropriate wavelength. Irradiation of the PS causes its transition to the excited singlet state and, via intersystem crossing; the PS reaches its triplet state. Electron transfer occurs upon relaxation to the ground state. This process can take place in two ways distinguished as type I and II mechanisms [5

• class of compounds known as squaraines [13][14][15][16][17][18]. Squaraines are a promising class of fluorescent dyes for PDT. In the past, squaraines showed a very low intersystem-crossing efficiency, leading to the premature conclusion that these dyes cannot be used in PDT [19]. Santos et al. showed

• that the intersystem-crossing efficiency of squaraines can be remarkably increased by incorporation of heavy atoms like selenium or sulfur and the addition of long aliphatic side chains [20][21]. The enhanced intersystem-crossing efficacy due to spin-orbital interactions makes modified squaraines a

Synthesis of 2,1-benzisoxazole-3(1H)-ones by base-mediated photochemical N–O bond-forming cyclization of 2-azidobenzoic acids

• Daria Yu. Dzhons and
• Andrei V. Budruev

Beilstein J. Org. Chem. 2016, 12, 874–881, doi:10.3762/bjoc.12.86

• through a 1,5-electrocyclization reaction [56][57]. Nonreacted singlet nitrenes A may undergo intersystem crossing (ISC) into the less reactive triplet state (Scheme 1, intermediate D). Although a multiplicity change is a spin-forbidden transition, it can be partially allowed in some cases. According to

• intersystem crossing for the initially formed singlet nitrenes (Scheme 1, intermediate A) to the triplet state (Scheme 1, intermediate D), thus resulting in decreased yields of the cyclization products 2c–e. In these cases, the formation of the triplet nitrene D should lead to increased yields of primary

Indenopyrans – synthesis and photoluminescence properties

• Andreea Petronela Diac,
• Ana-Maria Ţepeş,
• Albert Soran,
• Ion Grosu,
• Anamaria Terec,
• Jean Roncali and
• Elena Bogdan

Beilstein J. Org. Chem. 2016, 12, 825–834, doi:10.3762/bjoc.12.81

• the cis isomers 2''b (313 nm, in acetonitrile). All derivatives 2a–d showed an intense emission in acetonitrile in the range 380–393 nm (Figure 4, Table 3), while for the cis isomer 3''b a weaker emission was observed. This may be explained by a less extended conjugation and an intersystem-crossing

Probing multivalency in ligand–receptor-mediated adhesion of soft, biomimetic interfaces

• Stephan Schmidt,
• Hanqing Wang,
• Daniel Pussak,
• Simone Mosca and
• Laura Hartmann

Beilstein J. Org. Chem. 2015, 11, 720–729, doi:10.3762/bjoc.11.82

• (Scheme 1). It is known that benzophenone can absorb the energy of photons to excite the electron in its carbonyl group from ground state (S0) to the excited state (S1) or (S2) depending on the wavelength used. Subsequently, the excited electron can go to the triple state (T1) through intersystem crossing

A small azide-modified thiazole-based reporter molecule for fluorescence and mass spectrometric detection

• Stefanie Wolfram,
• Hendryk Würfel,
• Stefanie H. Habenicht,
• Christine Lembke,
• Phillipp Richter,
• Eckhard Birckner,
• Rainer Beckert and
• Georg Pohnert

Beilstein J. Org. Chem. 2014, 10, 2470–2479, doi:10.3762/bjoc.10.258

• . However, introduction of these heavy atom substituents in a fluorophore is challenging since it often results in decreased fluorescence due to intersystem crossing [26]. When working with reversed-phase LC–MS not only a specific isotopic pattern but also balanced polarity of the reporter is required

Photorelease of phosphates: Mild methods for protecting phosphate derivatives

• Sanjeewa N. Senadheera,
• Abraham L. Yousef and
• Richard S. Givens

Beilstein J. Org. Chem. 2014, 10, 2038–2054, doi:10.3762/bjoc.10.212

• the developing anionic charge on the departing nucleofuge. The resulting biradical 31, which must be a triplet by Wigner’s spin rule [47] is formed from the chromophore while on the excited state PES. Intersystem crossing (isc) to a diradicaloid ground state intermediate 32 (vide infra) is followed by

• acidic proton (especially for singlet state reactions). The carbonyl appendage, however, must be responsible for the enhanced heterolysis efficiency [28][29][38] and may influence the formation of the triplet excited state through intersystem crossing (isc) [26] which is the origin of the heterolysis and

• intersystem crossing in the 2,6-HNA platform and strong fluorescence of the 2,6-HNA chromophore (Figure 2) also diminishes formation of the triplet and, thus, its participation in a photo-Favorskii rearrangement. Finally, an indication of the photostability of the 2,6-HNA derivatives had earlier precedence in

Synthesis of new, highly luminescent bis(2,2’-bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4-thiadiazole and 1,2,4-triazole

• Anastasia S. Kostyuchenko,
• Vyacheslav L.Yurpalov,
• Aleksandra Kurowska,
• Wojciech Domagala,
• Adam Pron and
• Alexander S. Fisyuk

Beilstein J. Org. Chem. 2014, 10, 1596–1602, doi:10.3762/bjoc.10.165

• increasing atomic number of the heteroatom of the azole unit is a clear manifestation of the heavy atom effect [35]. The proximity and availability of higher energy 3d levels in sulfur facilitates radiationless relaxation modes of the excited electron. Enhanced spin–orbit coupling opens up intersystem

• crossing channels as well, making the thermal decay pathway accessible. The hindering of these decay modes in the oxadiazole derivatives 13 and 14 doubles their quantum yield. For the triazole derivative 18 the quantum yield is even nearly triple that of 15, but this enhancement should also be traced to

Tailoring of organic dyes with oxidoreductive compounds to obtain photocyclic radical generator systems exhibiting photocatalytic behavior

• Christian Ley,
• Julien Christmann,
• Ahmad Ibrahim,
• Luciano H. Di Stefano and
• Xavier Allonas

Beilstein J. Org. Chem. 2014, 10, 936–947, doi:10.3762/bjoc.10.92

• a dye (PS) with an electron acceptor (A) is depicted. After absorption of actinic light (hν), the PS reaches its singlet excited state (1PS*) and after intersystem crossing (kISC), its triplet excited state (3PS*). From both these excited states, an electron transfer can occur from the PS to A (with

• rate constants of singlet and triplet state deactivation to the ground state, respectively; kISC the rate constant of the intersystem crossing from 1PS to 3PS; 1kq/A, 3kq/A, (1kq/D, 3kq/D) the bimolecular electron transfer rate constant of the singlet and triplet excited state of the PS by the acceptor

• . Intersystem crossing rate constant kISC was obtained from the triplet state quantum yield and singlet state lifetime according to [59]: which leads to: and to At this RB concentration, and in the absence of quencher, the triplet state lifetime was measured around 80 µs, leading to kdes3= 1.25·104 M−1s−1

Studies on the photodegradation of red, green and blue phosphorescent OLED emitters

• Susanna Schmidbauer,
• Andreas Hohenleutner and
• Burkhard König

Beilstein J. Org. Chem. 2013, 9, 2088–2096, doi:10.3762/bjoc.9.245

• effectively convert singlet into triplet states via fast intersystem crossing. The recombination of electron–hole pairs generates singlet and triplet excitons in a ratio of 1:3 which means that the use of phosphorescent devices can give up to 4 times higher efficiencies than those based on fluorescent

The chemistry of amine radical cations produced by visible light photoredox catalysis

• Jie Hu,
• Jiang Wang,
• Theresa H. Nguyen and
• Nan Zheng

Beilstein J. Org. Chem. 2013, 9, 1977–2001, doi:10.3762/bjoc.9.234

• share one common characteristic: a facile intersystem crossing (ISC) that allows the conversion of the initially formed singlet photoexcited state to the relatively long-lived triplet photoexcited state. The triplet photoexcited state’s long lifetime permits it to engage in single-electron transfer with

Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution

• Hai Ming Wang and
• Gerhard Wenz

Beilstein J. Org. Chem. 2013, 9, 1858–1866, doi:10.3762/bjoc.9.217

• spin-orbit coupling interactions between states of different spin multiplicities and consequently facilitate intersystem crossing. However, supramolecular control of the packing of ACE leads to a significant improvement of the stereoselectivity. ACE was complexed in a cavitand nanocapsule [32] and in a

• < 10−3% and mainly leading to the anti-HH dimer [39]. In contrast, polar protic solvents, like water, increase both the quantum yield and the amount of the syn-HH dimer, exemplified in Table 3. The singlet state has a very short lifetime because of rapid intersystem crossing and self-quenching and it

• atom effect of the S-atoms of CD derivatives 1–7 should facilitate intersystem crossing to the triplet state and therefore support the formation of the anti-HH dimer. Because this preference does not hold true in this case, especially for host 2, the multiplicity of the excited state seems not to be

Electron self-exchange activation parameters of diethyl sulfide and tetrahydrothiophene

• Martin Goez and
• Martin Vogtherr

Beilstein J. Org. Chem. 2013, 9, 1448–1454, doi:10.3762/bjoc.9.164

• species, an ”automatic” labeling with nonequilibrium magnetizations is also feasible by utilizing the CIDNP [5][6][7][8][9][10] effect (chemically induced dynamic nuclear polarization). CIDNP arises through a complex interplay of nuclear-spin-selective intersystem crossing and electron-spin-selective

• . During their excursions, the differential precession of their electron spins causes intersystem crossing with a rate that depends on the spin states of their nuclei through the hyperfine interactions; upon reencounter, a chemical reaction serves to distinguish between singlet and triplet pairs (usually

• triplet energy (222 kJ/mol [32]) is only lower by less than 90 kJ/mol. Its first excited singlet state has a lifetime of 2.9 ns [32], so reacts only marginally with the millimolar sulfide concentrations used in our experiments, but its triplet state (intrinsic intersystem-crossing efficiency, 0.48 [32

Spin state switching in iron coordination compounds

• Philipp Gütlich,
• Ana B. Gaspar and
• Yann Garcia

Beilstein J. Org. Chem. 2013, 9, 342–391, doi:10.3762/bjoc.9.39

• the spin-allowed but parity-forbidden transition to the 1T1 and 1T2 ligand field states. These decay fast in two consecutive intersystem crossing processes, to the spin triplet states 3T1,2 and finally to the 5T2 state. Two factors are favorable for the occurrence of LIESST: (i) The spin triplet

• states 3T1,2 are placed energetically lower than the 1T1 and 1T2 ligand field states; (ii) The double intersystem crossing decay path is favored by spin–orbit coupling and therefore faster than the direct decay path back to 1A1. The decay of the 5T2 state to the 1A1 state is highly spin- and parity

• sample with red light (820 nm from a Krypton laser), whereby the metastable 5T2 state (“LIESST state”) is excited to the 5Eg state, which decays fast – again favored by spin–orbit coupling – by double intersystem crossing via 3T1,2 states to the LS (1A1) state [149]. The LIESST effect has mostly been

A simple and efficient dual optical signaling chemodosimeter for toxic Hg(II)

• Sabir H. Mashraqui,
• Sapna A. Tripathi,
• Sushil S. Ghorpade and
• Smita R. Britto

Beilstein J. Org. Chem. 2012, 8, 1352–1357, doi:10.3762/bjoc.8.155

• photostable fluorophore [52], has been designed to function as metal ion and anion sensor [53][54][55][56][57]. In contrast to moderately fluorescent acridone, its thione analog is poorly emissive presumably on account of the intersystem crossing process of the C=S bonding [58]. Keeping this in mind, we have

Continuous flow photolysis of aryl azides: Preparation of 3H-azepinones

• Farhan R. Bou-Hamdan,
• François Lévesque,
• Alexander G. O'Brien and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2011, 7, 1124–1129, doi:10.3762/bjoc.7.129

• expansion of 12, via 2H-azirine 3, affords didehydroazepine 4, which can be trapped by variety of nucleophiles to provide the corresponding azepine 5. Alternatively, intersystem crossing (ISC) of 12 gives rise to 32, which can dimerize to form diazo compound 6. Performing the reaction in the presence of

Fine-tuning alkyne cycloadditions: Insights into photochemistry responsible for the double-strand DNA cleavage via structural perturbations in diaryl alkyne conjugates

• Wang-Yong Yang,
• Samantha A. Marrone,
• Nalisha Minors,
• Diego A. R. Zorio and
• Igor V. Alabugin

Beilstein J. Org. Chem. 2011, 7, 813–823, doi:10.3762/bjoc.7.93

• photophysical step and the involvement of PET from 1,4-cyclohexadiene (1,4-CHD) to the enediyne excited singlet state. In contrast, substituents that accelerate the intersystem crossing (ISC) through a “phantom state” effect [53][54][55] direct reactivity along an alternative triplet cycloaddition pathway. Our

The arene–alkene photocycloaddition

• Ursula Streit and
• Christian G. Bochet

Beilstein J. Org. Chem. 2011, 7, 525–542, doi:10.3762/bjoc.7.61

• intersystem crossing by the heavy-atom effect, and thus decreases the singlet excited-state lifetime of the arene. Mattay considered this as direct proof that the addition of benzene to 1,3-dioxoles takes place primarily via the singlet excited-state of benzene. Ferree et al. had earlier provided evidence

Photoinduced electron-transfer chemistry of the bielectrophoric N-phthaloyl derivatives of the amino acids tyrosine, histidine and tryptophan

• Axel G. Griesbeck,
• Jörg Neudörfl and
• Alan de Kiff

Beilstein J. Org. Chem. 2011, 7, 518–524, doi:10.3762/bjoc.7.60

• photoinduced electron-transfer (PET) reactions. N-Alkylated phthalimides typically absorb in the 295 nm region with extinction coefficients around 103. The quantum yields for intersystem crossing ФISC significantly change with the substitution on the imide nitrogen, e.g., ФISC = 0.5 for N-isobutylphthalimide

Effects of anion complexation on the photoreactivity of bisureido- and bisthioureido-substituted dibenzobarrelene derivatives

• Heiko Ihmels and
• Jia Luo

Beilstein J. Org. Chem. 2011, 7, 278–289, doi:10.3762/bjoc.7.37

• intersystem crossing (ISC) process exists for the excited chromophore 1h that directs the photoreaction predominately to the triplet pathway. The 3,5-bis(trifluoromethyl)phenyl substituent may be responsible for the ISC, because m-bis(trifluoromethyl)benzene has an ISC quantum yield of ΦISC = 0.12 (λex = 254