Deciphering the Microdroplet Acceleration Factors of Aza-Michael Addition Reactions.

Microdroplet chemistry is emerging as a great tool for accelerating reactions by several orders of magnitude. Several unique properties such as extreme pHs, interfacial electric fields (IEFs), and partial solvation have been reported to be responsible for the acceleration; however, which factor plays the key role remains elusive. Here, we performed quantum chemical calculations to explore the underlying mechanisms of an aza-Michael addition reaction between methylamine and acrylamide. We showed that the acceleration in methanol microdroplets results from the cumulative effects of several factors. The acidic surface of the microdroplet plays a dominating role, leading to a decrease of ∼9 kcal/mol in the activation barrier. We speculated that the dissociation of both methanol and trace water contributes to the surface acidity. An IEF of 0.1 V/Šcan further decrease the barrier by ∼2 kcal/mol. Partial solvation has a negligible effect on lowering the activation barrier in microdroplets but can increase the collision frequency between reactants. With acidity revealed to be the major accelerating factor for methanol droplets, reactions on water microdroplets should have even higher rates because water is more acidic. Both theoretically and experimentally, we confirmed that water microdroplets significantly accelerate the aza-Michael reaction, achieving an acceleration factor that exceeds 107. This work elucidates the multifactorial influences on the microdroplet acceleration mechanism, and with such detailed mechanistic investigations, we anticipate that microdroplet chemistry will be an avenue rich in opportunities in the realm of green synthesis.

Two Key Descriptors for Designing Second Near-Infrared Dyes and Experimental Validation.

Second near-infrared (NIR-II) optical imaging technology has emerged as a powerful tool for diagnostic and image-guided surgery due to its higher imaging contrast. However, a general strategy for efficiently designing NIR-II organic molecules is still lacking, because NIR-II dyes are usually difficult to synthesize, which has impeded the rapid development of NIR-II bioprobes. Herein, based on the theoretical calculations on 62 multiaryl-pyrrole (MAP) systems with spectra ranging from the visible to the NIR-II region, a continuous red shift of the spectra toward the NIR-II region could be achieved by adjusting the type and site of substituents on the MAPs. Two descriptors (ΔEgs and µgs) were identified as exhibiting strong correlations with the maximum absorption/emission wavelengths, and the descriptors could be used to predict the emission spectrum in the NIR-II region only if ΔEgs ≤ 2.5 eV and µgs ≤ 22.55 D. The experimental absorption and emission spectra of ten MAPs fully confirmed the theoretical predictions, and biological imaging in vivo of newly designed MAP23-BBT showed high spatial resolution in the NIR-II region in deep tissue angiography. More importantly, both descriptors of ΔEgs and µgs have shown general applicability to most of the reported donor-acceptor-donor-type non-MAP NIR-II dyes. These results have broad implications for the efficient design of NIR-II dyes.

Incorporation of a Boron-Nitrogen Covalent Bond Improves the Charge-Transport and Charge-Transfer Characteristics of Organoboron Small-Molecule Acceptors for Organic Solar Cells.

An organoboron small-molecular acceptor (OSMA) MB←N containing a boron-nitrogen coordination bond (B←N) exhibits good light absorption in organic solar cells (OSCs). In this work, based on MB←N, OSMA MB-N, with the incorporation of a boron-nitrogen covalent bond (B-N), was designed. We have systematically investigated the charge-transport properties and interfacial charge-transfer characteristics of MB-N, along with MB←N, using the density functional theory (DFT) and the time-dependent density functional theory (TD-DFT). Theoretical calculations show that MB-N can simultaneously boost the open-circuit voltage (from 0.78 V to 0.85 V) and the short-circuit current due to its high-lying lowest unoccupied molecular orbital and the reduced energy gap. Moreover, its large dipole shortens stacking and greatly enhances electron mobility by up to 5.91 × 10-3 cm2·V-1·s-1. Notably, the excellent interfacial properties of PTB7-Th/MB-N, owing to more charge transfer states generated through the direct excitation process and the intermolecular electric field mechanism, are expected to improve OSCs performance. Together with the excellent properties of MB-N, we demonstrate a new OSMA and develop a new organoboron building block with B-N units. The computations also shed light on the structure-property relationships and provide in-depth theoretical guidance for the application of organoboron photovoltaic materials.

The Integration of the Metabolome and Transcriptome for Dendrobium nobile Lindl. in Response to Methyl Jasmonate.

Dendrobium nobile Lindl., as an endangered medicinal plant within the genus Dendrobium, is widely distributed in southwestern China and has important ecological and economic value. There are a variety of metabolites with pharmacological activity in D. nobile. The alkaloids and polysaccharides contained within D. nobile are very important active components, which mainly have antiviral, anti-tumor, and immunity improvement effects. However, the changes in the compounds and functional genes of D. nobile induced by methyl jasmonate (MeJA) are not clearly understood. In this study, the metabolome and transcriptome of D. nobile were analyzed after exposure to MeJA. A total of 377 differential metabolites were obtained through data analysis, of which 15 were related to polysaccharide pathways and 35 were related to terpenoids and alkaloids pathways. Additionally, the transcriptome sequencing results identified 3256 differentially expressed genes that were discovered in 11 groups. Compared with the control group, 1346 unigenes were differentially expressed in the samples treated with MeJA for 14 days (TF14). Moreover, the expression levels of differentially expressed genes were also significant at different growth and development stages. According to GO and KEGG annotations, 189 and 99 candidate genes were identified as being involved in terpenoid biosynthesis and polysaccharide biosynthesis, respectively. In addition, the co-expression analysis indicated that 238 and 313 transcription factors (TFs) may contribute to the regulation of terpenoid and polysaccharide biosynthesis, respectively. Through a heat map analysis, fourteen terpenoid synthetase genes, twenty-three cytochrome P450 oxidase genes, eight methyltransferase genes, and six aminotransferase genes were identified that may be related to dendrobine biosynthesis. Among them, one sesquiterpene synthase gene was found to be highly expressed after the treatment with MeJA and was positively correlated with the content of dendrobine. This study provides important and valuable metabolomics and transcriptomic information for the further understanding of D. nobile at the metabolic and molecular levels and provides candidate genes and possible intermediate compounds for the dendrobine biosynthesis pathway, which lays a certain foundation for further research on and application of Dendrobium.

Total Synthesis of (+)-Mutilin: A Transannular [2+2] Cycloaddition/Fragmentation Approach.

A new and enantioselective total synthesis of the diterpenoid (+)-mutilin is described. Following a Claisen rearrangement approach to construct the 6,9-bicycle, a transannular [2+2] photocycloaddition and the ensuing ring-opening reaction were implemented to forge the characteristic 5-6-8 propellane-like skeleton. Subsequent late-stage alkylations and reduction completed the synthesis.

Recent Progress of Diatomic Catalysts: General Design Fundamentals and Diversified Catalytic Applications.

In recent years, some experiments and theoretical work have pointed out that diatomic catalysts not only retain the advantages of monoatomic catalysts, but also introduce a variety of interactions, which exceed the theoretical limit of catalytic performance and can be applied to many catalytic fields. Here, the interaction between adjacent metal atoms in diatomic catalysts is elaborated: synergistic effect, spacing enhancement effect (geometric effect), and electronic effect. With regard to the classification and characterization of various new diatomic catalysts, diatomic catalysts are classified into four categories: heteronuclear/homonuclear, with/without carbon carriers, and their characterization measures are introduced and explained in detail. In the aspect of preparation of diatomic catalysts, the widely used atomic layer deposition method, metal-organic framework derivative method, and simple ball milling method are introduced, with emphasis on the formation mechanism of diatomic catalysts. Finally, the effective control strategies of four diatomic catalysts and the key applications of diatomic catalysts in electrocatalysis, photocatalysis, thermal catalysis, and other catalytic fields are given.

Theoretical insights into photo-induced isomerization mechanisms of phenylsulfinyl radical PhSO˙.

Sulfinyl radicals (R-SO˙) play important roles in lots of reactions, while the isomer oxathiyl radicals (R-OS˙) and the isomerization between them are rarely observed due to the poor stability of R-OS˙. In this work, the complete active space self-consistent field (CASSCF) and its multi-state second order perturbation (MS-CASPT2) methods were employed to study the photo-induced reaction mechanisms of phenylsulfinyl radical PhSO˙ 1 and its isomer phenoxathiyl radical PhOS˙ 2. Our results show that 1 and 2 have similar singly occupied molecular orbitals in the ground state but different properties in the excited state, which determine their diverse behaviors after irradiation. Radical 1 can generate 2 by light irradiation, but 2 produces isomerization product 3 (2-hydroxyphenylthiyl radical) and ring-opening product 4 (acyclic thioketoketene radical) in two paths via S atom migration intermediate Int1 (2-carbonylcyclohexadienthiyl radical). The former path involves consequent hydrogen shift reactions with a strongly exothermic process while the latter path involves both ring-expansion and ring-opening processes with a high barrier, resulting in a structural and energetic preference for the former path. Moreover, we revealed several conical intersections that participate in the reactions and facilitate the photochemical processes. Our calculations not only remain consistent with and clarify the experimental observations (X. Zeng, et al., J. Am. Chem. Soc., 2018, 140(31), 9972-9978) but also enrich the knowledge of sulfinyl radicals and isomer oxathiyl radicals.

A π-extended triphenylamine based dopant-free hole-transporting material for perovskite solar cells via heteroatom substitution.

The triphenylamine (TPA) group is an important molecular fragment that has been widely used to design efficient hole-transporting materials (HTMs). However, the applicability of triphenylamine derived HTMs that exhibit low hole mobility and conductivity in commercial perovskite solar cells (PSCs) has been limited. To aid in the development of highly desirable TPA-based HTMs, we utilized a combination of density functional theory (DFT) and Marcus electron transfer theory to investigate the effect of heteroatoms, including boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, arsenic, and selenium atoms, on the energy levels, optical properties, hole mobility, and interfacial charge transfer behaviors of a series of HTMs. Our computational results revealed that compared with the commonly referenced OMeTPA-TPA molecule, most heteroatoms lead to deeper energy levels. Furthermore, these heteroatom-based HTMs exhibit improved hole mobility due to their more rigid molecular structures. More significantly, these heteroatoms also enhance the interface interaction in perovskite/HTM systems, resulting in a larger internal electric field. Our work represents a new approach that aids in the understanding and designing of more efficient and better performing HTMs, which we hope can be used as a platform to propel the developmental commercialization of these highly desirable PSCs.

Sequence-selective recognition of cationic amphipathic tripeptides with similar structures in aqueous solutions by cucurbit[7]uril.

Sequence-selective recognition of cationic amphipathic peptides by synthetic receptors is significant to biological applications, but it is still a great challenging task. Here we first study the binding characteristics of receptor cucurbit[7]uril (CB[7]) to the smallest aromatic tripeptides X1GG (X1 = tryptophan (W), phenylalanine (F), and tyrosine (Y)) and basic tripeptides X2GG (X2 = arginine (R), lysine (K), and histidine (H)) by molecular dynamics simulations. The study indicates that the sidechains of aromatic X1 residues can be encapsulated into the CB[7] cavity, while the sidechains of basic X2 residues prefer to locate at the CB[7] portal. Based on that, we consider hydrophobic aromatic residues as the N-terminus, the smallest glycine (G) as the 2nd-residue and basic residues as the C-terminus, and design nine tripeptides X1GX2 (X1 = F, Y, W and X2 = H, K, R). We found that there is a great influence of the C-terminal basic residue of X1GX2 on binding with CB[7] due to the introduction of a new binding site between CB[7] and the sidechain of the C-terminal residue. Interestingly, CB[7] can differentiate WGR and WGK with similar structures efficiently because of their eight orders of magnitude difference in the association constant (Ka). Besides, for WGR, YGR, and YGK with a nanomolar binding affinity (Ka > 109 M-1), on reversing the sequence order of the 2nd-residue and 3rd-residue, their Ka reduces by about at least 1000-fold, implying the sequence dependence of CB[7] on recognizing these tripeptides. These results predict the potential applications of CB[7] in recognizing cationic amphipathic peptides.

Theoretical design of asymmetric A-D1A'D2-A type non-fullerene acceptors for organic solar cells.

The acceptor in organic solar cells (OSCs) is of paramount importance for achieving a high photovoltaic performance. Based on the well-known non-fullerene acceptor Y6, we designed a set of asymmetric A-D1A'D2-A type new acceptors Y6-C, Y6-N, Y6-O, Y6-Se, and Y6-Si by substituting the two S atoms of one thieno[3,2-b]thiophene unit with C, N, O, Se, and Si atoms, respectively. The electronic, optical, and crystal properties of Y6 and the designed acceptors, as well as the interfacial charge-transfer (CT) mechanisms between the donor PM6 and the investigated acceptors have been systematically studied. It is found that the newly designed asymmetric acceptors possess suitable energy levels and strong interactions with the donor PM6. Importantly, the newly designed acceptors exhibit enhanced light harvesting ability and more CT states with larger oscillator strengths in the 40 lowest excited states. Among the multiple CT mechanisms, the direct excitation of CT states is found to be more favored in the case of PM6/newly designed acceptors than that of PM6/Y6. This work not only offers a set of promising acceptors superior to Y6, but also demonstrates that designing acceptors with asymmetric structure could be an effective strategy to improve the performance of OSCs.

Designing Hole Transport Materials with High Hole Mobility and Outstanding Interface Properties for Perovskite Solar Cells.

Organic-inorganic halide perovskite solar cells (PSCs) have attracted much attention due to their rapid increase in power conversion efficiencies (PCEs), and many efforts are devoted to further improving the PCEs. Designing highly efficient hole transport materials (HTMs) for PSCs may be one of the effective ways. Herein we theoretically designed three new HTMs (FDT-N, FDT-O, and FDT-S) by introducing a nitrogen-phenyl group, an oxygen atom, and a sulfur atom into the spiro core of an experimentally synthesized HTM (FDT), respectively. And then we performed quantum chemical calculation to study their application potential. The results show that the devices with FDT-O and FDT-S instead of FDT may have higher open circuit voltages owing to their lower highest occupied molecular orbital (HOMO) energy levels. Moreover, FDT-S exhibits the best hole transport performance among the studied HTMs, which may be due to the significant HOMO-HOMO overlap in the hole hopping path with the largest transfer integral. Furthermore, the results on interface properties indicate that introducing oxygen and sulfur atoms can enhance the MAPbI3 /HTM interface interaction. The present work not only offers two promising HTMs (FDT-O and FDT-S) for PSCs but also provides theoretical help for subsequent research on HTMs.

Theoretical study on the photochemistry of furoylazides: Curtius rearrangement and subsequent reactions.

Organic azides are an efficient source of nitrenes, which serve as vigorous intermediates in many useful organic reactions. In this work, the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods were employed to study the photochemistry of 2-furoylazide 1 and 3-furoylazide 5, including the Curtius rearrangement to two furylisocyanates (3 and 7) and subsequent reactions to the final product cyanoacrolein 9. Our calculations show that the photoinduced Curtius rearrangement of the two furoylazides takes place through similar stepwise mechanisms via two bistable furoylnitrenes 2 and 6. However, the decarbonylation and ring-opening process of 7 to 9 prefers a stepwise mechanism involving the 3-furoylnitrene intermediate 8, while 3 to 9 goes in a concerted asynchronous way without the corresponding 2-furoylnitrene intermediate 4. Importantly, we revealed that several conical intersections play key roles in the photochemistry of furoylazides. Our results are not only consistent and also make clear the experimental observations (X. Zeng, et al., J. Am. Chem. Soc., 2018, 140, 10-13), but additionally provide important information on the chemistry of furoylazides and nitrenes.

Understanding the effects of the co-sensitizing ratio on the surface potential, electron injection efficiency, and Förster resonance energy transfer.

Multiple absorbers that function in different absorption regions (near infra-red (NIR) and UV-Visible (UV-Vis)) have been widely used in solar cell applications to enhance the light-harvesting. Herein, two special co-sensitizing Models 1 and 2, which feature either saturated dye IQ21 or saturated co-sensitizer S2, have been added to a TiO2 surface to explore the effect of the altered sensitizing sequence, namely the co-sensitizing ratio of IQ21/S2 and S2/IQ21 on the electrostatic potential variation (ΔV), electron injection efficiency (ηinj'), and Förster resonance energy transfer (FRET), using density functional theory and first-principle molecular dynamics simulations. The ΔV related to the open-circuit voltage (Voc) is insensitive in both Models 1 and 2. However, the absorption (λabs) and ηinj' associated with the short-circuit density (Jsc) display a significant deviation (the λabs for 1 is red-shifted compared to that of 2, and the ηinj' for 1 is improved by 56%). Meanwhile, Model 1 manifests a suppressed FRET and potentially favors co-sensitizer S2 functioning as the electron-injector and not the energy-donor. Another two possible Models 3 and 4 that feature a reduced adsorption of IQ21 and S2 relative to 1 and 2 were considered further, and the result mirrors the main trend in 1 and 2, except for the ηinj'. Overall, it implies that sensitizing a larger absorber with NIR features to saturate it first, then introducing a smaller absorber with UV-Vis features, can potentially improve the electron injection and diminish electron-hole recombination considerably. Our results provide a comprehensive analysis of the active role of an optimized sensitizing sequence to improve the conversion efficiency.

Reconfigurable Assembly of Active Liquid Metal Colloidal Cluster.

We report the reconfigurable assembly of rod-shaped eutectic gallium-indium alloy (EGaIn) liquid metal colloidal motors by mimicking the growth behavior of a dandelion. EGaIn nanorods with a diameter of 210 nm and a length of 850 nm were synthesized via an ultrasound-assisted physical dispersion method. The nanorods possess a core-shell structure with a 30 nm GaOOH shell and zero-valent liquid core. The EGaIn motors move autonomously at a speed of 41.2 µm s-1 under an acoustic field. By modulating the frequency of the applied acoustic field, the EGaIn colloidal motors self-organize into various striped and circular patterns, followed by a flower-like cluster. The dandelion-like EGaIn colloidal motor clusters move collectively and redisperse when the applied acoustic frequency is changed. Numerical simulations reveal that the flower-like clusters are created by the acoustic propulsion in combination with steric repulsion and hydrodynamics.

A peri-Xanthenoxanthene Centered Columnar-Stacking Organic Semiconductor for Efficient, Photothermally Stable Perovskite Solar Cells.

Modulating the structure and property of hole-transporting organic semiconductors is of paramount importance for high-efficiency and stable perovskite solar cells (PSCs). This work reports a low-cost peri-xanthenoxanthene based small-molecule P1, which is prepared at a total yield of 82 % using a three-step synthetic route from the low-cost starting material 2-naphthol. P1 molecules stack in one-dimensional columnar arrangement characteristic of strong intermolecular π-π interactions, contributing to the formation of a solution-processed, semicrystalline thin-film exhibiting one order of magnitude higher hole mobility than the amorphous one based on the state-of-the art hole-transporter, 2,2-7,7-tetrakis(N,N'-di-paramethoxy-phenylamine 9,9'-spirobifluorene (spiro-OMeTAD). PSCs employing P1 as the hole-transporting layer attain a high efficiency of 19.8 % at the standard AM 1.5 G conditions, and good long-term stability under continuous full sunlight exposure at 40 °C.

Theoretical study on the regioselective photoisomerization of asymmetric N,C-chelate organoboron compounds.

Herein, the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods combined with time-dependent density functional theory (TD-DFT) calculations were employed to investigate the isomerization reaction mechanisms of an asymmetric N,C-chelate organoboron compound, B(ppy)MesPh, in the ground (S0) state and the first singlet excited (S1) state. Our calculations show that isomerizations proceed via different pathways in the S0 and S1 states,; however, the energy barriers for mesityl isomerization are higher than those for phenyl isomerization in both states; this is in good agreement with the experimentally observed regioselectivity (S. Wang, et al. Angew. Chem., Int. Ed., 2017, 56, 6093-6097). Photoisomerization is motivated by charge transfer from two phenyl rings to the pyridyl moiety and initiated by the cleavage of the B-Cppy bond, followed by the formation of a boracyclopropane ring via an (S1/S0)X conical intersection and a biradical intermediate. Both steric and electronic features were found to be important for regioselective photoisomerization. Our results not only shed light on the experimental observations, but also provide valuable details on the excited state dynamics of organoboron compounds and can facilitate further syntheses and applications.

Crepidatumines C and D, Two New Indolizidine Alkaloids from Dendrobium crepidatum Lindl. ex Paxt.

Two new indolizidine alkaloids, crepidatumines C (1) and D (2), together with crepidine (3), isocrepidamine (4), and crepidamine (5) were isolated from the Dendrobium crepidatum Lindl. ex Paxt. X-ray diffraction experiments established the absolute configurations of known compounds 3 and 4. The planar structures and relative configurations of new compounds 1 and 2 were elucidated by extensive spectra analysis including HR-ESI-MS, NMR (1H, 13C, 1H-1H COSY, HSQC, HMBC, and NOESY spectra), and the absolute configurations of 1 and 2 were suggested on the basis of possible biosynthetic pathways. The biological results confirmed that isocrepidamine (4) displayed a potent hypoglycemic effect in vitro without cytotoxicity.

Self-Catalytic Reaction of SO3 and NH3 To Produce Sulfamic Acid and Its Implication to Atmospheric Particle Formation.

Sulfur trioxide (SO3) is one of the most active chemical species in the atmosphere, and its atmospheric fate has profound implications to air quality and human health. The dominant gas-phase loss pathway for SO3 is generally believed to be the reaction with water molecules, resulting in sulfuric acid. The latter is viewed as a critical component in the new particle formation (NPF). Herein, a new and competitive loss pathway for SO3 in the presence of abundant gas-phase ammonia (NH3) species is identified. Specifically, the reaction between SO3 and NH3, which produces sulfamic acid, can be self-catalyzed by the reactant (NH3). In dry and heavily polluted areas with relatively high concentrations of NH3, the effective rate constant for the bimolecular SO3-NH3 reaction can be sufficiently fast through this new loss pathway for SO3 to become competitive with the conventional loss pathway for SO3 with water. Furthermore, this study shows that the final product of the reaction, namely, sulfamic acid, can enhance the fastest possible rate of NPF from sulfuric acid and dimethylamine (DMA) by about a factor of 2. An alternative source of stabilizer for acid-base clustering in the atmosphere is suggested, and this new mechanism for NPF has potential to improve atmospheric modeling in highly polluted regions.

Effect of π-bridge units on properties of A-π-D-π-A-type nonfullerene acceptors for organic solar cells.

Acceptor-π-donor-π-acceptor (A-π-D-π-A)-types of small molecules are very promising nonfullerene acceptors to overcome the drawbacks of fullerene derivatives such as the weak absorption ability and electronic adjustability. However, only few attempts have been made to develop π-bridge units to construct highly efficient acceptors in OSCs. Herein, taking the reported acceptor P1 as a reference, five small-structured acceptors (P2, P3, P4, P5, and P6) have been designed via the replacement of the π-bridge unit. A combination of quantum chemistry and Marcus theory approaches is employed to investigate the effect of different π-bridge units on the optical, electronic, and charge transport properties of P1-P6. The calculation results show that the designed molecules P2 and P5 can become potential acceptor replacements of P1 due to their red-shifted absorption bands, appropriate energy levels, low exciton binding energy, and high electron affinity and electron mobility. Additionally, compared with P3HT/P1, P3HT/P2 and P3HT/P5 exhibit stronger and wider absorption peaks, larger electron transfer distances (DCT), greater transferred charge amounts (Δq), and smaller overlaps (Λ), which shows that P2 and P5 have more significant electron transfer characteristics and favorable exciton dissociation capabilities for enhancing the short-circuit current density (JSC) and thus, they are potential acceptors in OSCs.

Theoretical study of non-Hammett vs. Hammett behaviour in the thermolysis and photolysis of arylchlorodiazirines.

Arylchlorodiazirines (ACDA) are thermal and photochemical precursors of carbenes that form these molecules via nitrogen elimination. We have studied this reaction with multireference quantum chemical methods (CASSCF and CASPT2) for a series of ACDA derivatives with different substitution at the aromatic ring. The calculations explain the different reactivity trends found in the ground and excited state, with good correlation between the calculated barriers and the experimental reaction rates. The ground state mechanism can be described as a reverse cycloaddition with small charge transfer from the aromatic ring to the diazirine moiety. This is consistent with the lack of correlation between the Hammett σ descriptors and the experimental rates. In contrast, the excited state reaction is the cleavage of a single C-N bond mediated by small barriers of 4-6 kcal mol-1. The reaction path goes through a conical intersection with the ground state, which facilitates radiationless decay and explains the disappearance of the transient absorption signal measured experimentally. This leads to a diazomethane intermediate that ultimately yields the carbene. Electronically, excitation to S1 is characterized initially by significant charge transfer from the phenyl ring to the diazirine. The charge transfer is reversed during the C-N cleavage reaction, and this explains the preferential stabilization of the excited-state minimum by polar solvents and electron-donating substituents. Therefore, our calculations reproduce and explain the relationship found experimentally between the Hammett σ+ parameters and the life time of S1 (Y. L. Zhang, et al. J. Am. Chem. Soc., 2009, 131, 16652-16653).