Influence of solvent on carbene intersystem crossing rates

The influence of coordinating solvents on singlet-to-triplet carbene intersystem crossing (ISC) rates has been studied with diphenylcarbene (DPC) and para-biphenyltrifluoromethylcarbene (BpCCF 3) by using ultrafast time-resolved spectroscopy. DPC has a triplet ground state in all of the solvents considered, and the concentration of singlet carbene at equilibrium is too small to be measured. It is found that the lifetime of (1)DPC is extended in acetonitrile, benzene, tetrahydrofuran, dichloromethane, and halobenzene solvents relative to cyclohexane. The solvent effect does not well correlate with bulk measures of solvent polarity. The singlet-triplet energy separation of BpCCF 3 is close to zero. The data demonstrates that BpCCF 3 has a triplet ground state in benzene, fluorobenzene, and hexafluorobenzene. Halogenated solvents are found to dramatically retard the rate of ISC in (1)BpCCF 3. We postulate that the empty p orbital of a singlet carbene coordinates with a nonbonding pair of electrons of a halogen atom of the solvent to form a pseudoylide solvent complex, stabilize the singlet carbene, and decrease the singlet-triplet (S-T) energy gap. The "golden rule" of radiationless transitions posits that the smaller the energy gap between the two states, the faster their rate of interconversion. To explain the apparent violation of the golden rule of radiationless transitions for the carbene ISC processes monitored in this study, we propose that the significantly different specific solvation of the singlet and triplet carbenes imposes a Franck-Condon-like factor on the ISC process. Those solvents that most solvate the singlet carbene will also have the greatest structural difference between singlet carbene-solvent complex and their triplet spin isomer-solvent complex, the smallest S-T gap, and the slowest ISC rate. Alternatively, one can propose that a highly solvated singlet carbene must desolvate prior to ISC, and that this requirement decelerates the radiationless transition.     

On the intrinsic population of the lowest triplet state of thymine

The population of the lowest triplet state of thymine after near-UV irradiation has been established, on the basis of CASPT2//CASSCF quantum chemical calculations, to take place via three distinct intersystem crossing mechanisms from the initially populated singlet bright 1pipi* state. Two singlet-triplet crossings have been found along the minimum-energy path for ultrafast decay of the singlet state at 4.8 and 4.0 eV, involving the lowest 3npi* and 3pipi* states, respectively. Large spin-orbit coupling elements predict efficient intersystem crossing processes in both cases. Another mechanism involving energy transfer from the lowest 1npi* state with much larger spin-orbit coupling terms can also be proposed. The wavelength dependence measured for the triplet quantum yield of pyrimidine nucleobases is explained by the location and accessibility of the singlet-triplet crossing regions.     

Carbene stabilization by aryl substituents. Is bigger better?

The geometries and relative stabilities of the singlet and triplet states of phenyl- (Cs), diphenyl- (C2), 1-naphthyl- (Cs), di(1-naphthyl)- (C2), and 9-anthryl-substituted (Cs) carbenes were investigated at the B3LYP/6-311+G(d,p) + ZPVE level of density functional theory. The singlet-triplet energy separations (DeltaEST), 2.7, 2.9, 3.4, 3.7, and 5.7 kcal/mol, respectively, after including an empirical correction (2.8 kcal/mol) based on the error in the computed singlet-triplet gap for methylene versus experiment, are in good agreement with available experimental values. Consistent with literature reports, triplet di(9-anthryl)carbene has a linear, D2d symmetrical, allene structure with 1.336 A C=C bond lengths and considerable biradical character. B3LYP favors such cumulene biradical structures and triplet spin states and predicts a large (>15 kcal/mol) "di(9-anthryl)carbene" singlet-triplet (biradical) energy gap. The resonance stabilization of both singlet and triplet carbenes increases modestly with the size of the arene substituent and overall, (di)arylcarbenes, both singlet and triplet, are better stabilized by bigger substituents. For example, methylene is stabilized more by a naphthyl than a phenyl group (singlets, 26.6 versus 24.4; and triplets, 20.9 versus 18.1 kcal/mol, respectively). The carbene geometries are affected by both steric effects and arene-carbene orbital interactions (sigma-p and p-pi). For instance, the central angles at the carbene are widened by a second arene group, which leads to increased s-character and shorter carbene bond lengths (i.e., C-C, C-H). In general, the aromaticity of the substituted rings in triplet carbenes is most affected by the presence of the unpaired electrons.     

Solvent dependence of the 2-naphthyl(carbomethoxy)carbene singlet-triplet energy gap

The solvent dependence of the 2-naphthyl(carbomethoxy)carbene (2) singlet-triplet energy gap has been examined by time-resolved infrared (TRIR) and computational methods. The ground state of 2 changes from the triplet state in hexane to the singlet state in acetonitrile. Preferential stabilization of the singlet carbene is the result of its increased dipole moment in polar solvents. Variable-temperature TRIR experiments provide measurements of the enthalpic and entropic differences between (1)2 and (3)2 and suggest that solvent and geometry effects on the entropy of singlet and triplet carbenes can offset differences arising from spin multiplicity. B3LYP calculations using the polarizable continuum solvation model (PCM) reproduce the general trends in enthalpic differences seen experimentally.     

Conformational analysis of singlet-triplet state mixing in Paternò-Büchi diradicals

Conformational dependence of spin-orbit coupling (SOC) in flexible Paternò-Büchi (PB) diradicals has been studied with high-level ab initio methods using both (i) one-electron spin-orbit Hamiltonian with parametrized (effective) nuclear charges in conjunction with a state-averaged MCSCF wave function as implemented by Robb in Gaussian 98 and (ii) complete one- and two-electron SOC with a fully optimized MCSCF triplet wave function and frozen core singlet as implemented by Furlani in the GAMESS computational package. The ab initio results revealed two distinct areas of elevated SOC values, one corresponding to the region whereby a cisoid conformation in the C-C-O-C fragment brings the two odd-electron orbitals closer to each other, and the other area corresponding to the partially eclipsed conformation lacking direct overlap between the spin centers. In this second region the 1,4-electronic communication is mediated by the oxygen's 2p-lone pair, which is suitably oriented to play the role of a "relay-antenna". The other critical factor affecting the rate of intersystem crossing (ISC)--singlet-triplet energy separation--was computed utilizing a multireference CASSCF-MP2 method to include dynamic correlation effects. The largest singlet-triplet energy gap, approximately 2 kcal/mol, was found for a gauche conformer (also a minimum SOC conformation). Rotation about the central C-O bond either toward the fully eclipsed (0 degrees ) or the partially eclipsed (120 degrees ) conformations decreases the singlet-triplet gap while increasing the value of the SOC matrix element. These computational findings support the Griesbeck model for stereochemistry of triplet PB reactions and provide a rigorous basis for predicting the probability of ISC in diradicals separated by a partially conjugated spacer.     

Ultrafast UV-vis and IR studies of p-biphenylyl acetyl and carbomethoxy carbenes

The photochemistry of a p-biphenylyl diazo ester (BpCN2CO2CH3) and diazo ketone (BpCN2COCH3) were studied by ultrafast time-resolved UV-vis and IR spectroscopies. The excited states of these diazo compounds were detected and found to decay with lifetimes of less than 300 fs. The diazo ester produces singlet carbene with greater quantum efficiency than the ketone analogue due to competing Wolff rearrangement (WR) in the excited state of the diazo ketone. Carbene BpCCO2CH3 has a singlet-triplet gap that is close to zero in cyclohexane, but the triplet is the ground state. The two spin states are in rapid equilibrium in this solvent relative to reaction with cyclohexane. There is (for a carbene) a slow rate of singlet to triplet intersystem crossing (isc) in this solvent because the orthogonal singlet must rotate to a higher energy orientation prior to isc. In acetonitrile and in dichloromethane BpCCO2CH3 has a singlet ground state. Ketocarbene BpCCOCH3 has a singlet ground state in cyclohexane, in dichloromethane, and in acetonitrile and decays by WR to form a ketene detected by ultrafast IR spectroscopy in these solvents. Ketocarbenes have more stable singlet states, relative to carbene esters, because of the superior conjugation of the filled hybrid orbital of the carbene with the pi system of the carbonyl group, the same factor that makes methyl ketones more acidic than the analogous esters. The rate of WR of BpCCOCH3 is faster in cyclohexane than in dichloromethane and acetonitrile because of intimate solute-solvent interactions between the empty p orbital of the carbene and nonbonding electron pairs of heteroatoms of the solvent. These interactions stabilize the carbene and retard the rate of WR.     

Model studies of hydrogen atom addition and abstraction processes involving ortho-, meta-, and para-benzynes.

H-atom addition and abstraction processes involving ortho-, meta-, and para-benzyne have been investigated by multiconfigurational self-consistent field methods. The H(A) + H(B)...H(C) reaction (where r(BC) is adjusted to mimic the appropriate singlet-triplet energy gap) is shown to effectively model H-atom addition to benzyne. The doublet multiconfiguration wave functions are shown to mix the "singlet" and "triplet" valence bond structures of H(B)...H(C) along the reaction coordinate; however, the extent of mixing is dependent on the singlet-triplet energy gap (DeltaE(ST)) of the H(B)...H(C) diradical. Early in the reaction, the ground-state wave function is essentially the "singlet" VB function, yet it gains significant "triplet" VB character along the reaction coordinate that allows H(A)-H(B) bond formation. Conversely, the wave function of the first excited state is predominantly the "triplet" VB configuration early in the reaction coordinate, but gains "singlet" VB character when the H-atom is close to a radical center. As a result, the potential energy surface (PES) for H-atom addition to triplet H(B)...H(C) diradical is repulsive! The H3 model predicts, in agreement with the actual calculations on benzyne, that the singlet diradical electrons are not coupled strongly enough to give rise to an activation barrier associated with C-H bond formation. Moreover, this model predicts that the PES for H-atom addition to triplet benzyne will be characterized by a repulsive curve early in the reaction coordinate, followed by a potential avoided crossing with the (pi)1(sigma*)1 state of the phenyl radical. In contrast to H-atom addition, large activation barriers characterize the abstraction process in both the singlet ground state and first triplet state. In the ground state, this barrier results from the weakly avoided crossing of the dominant VB configurations in the ground-state singlet (S0) and first excited singlet (S1) because of the large energy gap between S0 and S1 early in the reaction coordinate. Because the S1 state is best described as the combination of the triplet X-H bond and the triplet H(B)...H(C) spin couplings, the activation barrier along the S0 abstraction PES will have much less dependence on the DeltaE(ST) of H(B)...H(C) than previously speculated. For similar reasons, the T1 potential surface is quite comparable to the S0 PES.     

2-(3,5-Dinitrophenyl)-1,3-dithiane carbanion: a benzylic anion with a low energy triplet state

Calculations at the DFT level predict that benzyl anions with strong π-electron-withdrawing groups in the meta position(s) have low energy diradical or triplet electronic states. Specifically, the 2-(3,5-dinitrophenyl)-1,3-dithiane carbanion is predicted to have nearly degenerate singlet and triplet states at the (U)B3LYP level as a free anion. Its lithium ion pair is predicted to be a ground-state triplet with a substantial (26 kcal/mol) singlet-triplet energy gap. Experiments on this anion using chemical trapping, NMR, and the Evans method strongly suggest that this anion is either a triplet or a ground-state singlet with a very low energy triplet state.     

Strained delocalized carbenoid ring systems — A theoretical investigation

A number of ring compounds containing a divalent carbon center (carbenes) have been studied usingab initio quantum chemical methods. The studied systems include: imidazol-2-ylidene, 4-pyranylidene, 9-xanthylidene, cyclohexa-2,5-dienylidene and 4-oxocyclohexa-2,5-dienylidene. Extended ANO type basis sets were used. Wave functions and energies were obtained with a multiconfigurational approach (CASSCF), where dynamic correlation effects are treated by using second-order perturbation theory (CASPT2).The singlet-triplet splitting has been found to depend linearly on the energy separation between the two carbene orbitals. All systems, where this splitting is larger than about 10 eV have been found to have a singlet ground state, while those with a smaller gap have a triplet ground state. A number of excited states have been characterized. Computed excitation energies are in agreement with experiment in cases where such information is available.     

Triplet ground state derivative of aza-m-xylylene diradical with large singlet-triplet energy gap

Organic molecules with a strong preference for triplet ground states, in which the triplet state is below the lowest singlet state by ≥10 kcal/mol, are typically short-lived and mostly detected as reactive intermediates. We now report a triplet ground state derivative of aza-m-xylylene diradical with a large singlet-triplet energy gap (ΔE(ST)) of ～10 kcal/mol, which is comparable to ΔE(ST) for the well-known reactive intermediate m-xylylene diradical. The aminyl diradical persists in solution at room temperature on the time scale of minutes.     

Study of singlet-triplet coupling in glyoxal by level anticrossing spectroscopy. VII. Complete assignment of the 00, 81, 6171 and 41 anticrossing spectra

In paper VI of this series, we have made the statistical analysis of the singlet-triplet coupling matrix elements for ten N_S = 0 singlet vibrational levels of glyoxal, without determining the triplet quantum numbers. In this paper we present the complete assignment (triplet rotational quantum numbers and vibrational symmetry) of each anticrossing observed from four singlet vibrational levels: 0⁰, 8¹, 6¹7¹ and 4¹ (which give respectively 36, 76, 155 and 145 anticrossings by 0 to 7.5 T scans). Therefore we determine the zero-field energy origin of most of the triplet vibrational levels which are located within 7 cm⁻¹ of the four singlet levels studied. Two kinds of selection rules are found: the first stemming from direct vibronic spin-orbit interactions and the second from indirect ones (involving an intermediate triplet state). About half of the anticrossings are due to direct vibronic spin-orbit interactions, the mean value of their matrix elements is more than ten times larger than indirect matrix elements and thus are dominant in ϱ〈V_st〉. In conclusion, we confirm that ISC in glyoxal is governed by direct vibronic spin-orbit interactions.     

2-Naphthyl(carbomethoxy)carbene revisited: combination of ultrafast UV-vis and infrared spectroscopic study

Ultrafast laser flash photolysis (310 nm) of methyl 2-napthyldiazoacetate (2-NpCN2CO2CH3) in acetonitrile or cyclohexane produces a diazo excited state which absorbs broadly in the visible region (tau = 300 fs). The decay of the excited diazo compound is accompanied by growth of the vibrationally excited singlet 2-naphthyl(carbomethoxy)carbene ((1)NpCCO2CH3). The singlet carbene absorbs at 360 and 470 nm. In acetonitrile these bands do not decay over 3 ns, but they do decay by approximately 50% of their original intensity in cyclohexane in 3 ns. It is concluded that (1)NpCCO2CH3 has a singlet ground state in acetonitrile but a triplet ground state in cyclohexane. Related experiments reveal a singlet ground state in Freon-113 and chloroform. This interpretation is supported by ultrafast IR spectroscopy, which confirms that only (1)NpCCO2CH3 is formed within 50 ps of the laser pulse rather than a singlet-triplet equilibrium mixture of carbene. The planar singlet relaxes to the preferred perpendicular singlet over a few tens of picoseconds, as evidenced by a red shift of the carbonyl stretching vibration. Although our data agrees with previous studies, its interpretation is somewhat altered.     

Hydrogen Bonding Switches the Spin State of Diphenylcarbene from Triplet to Singlet

Spin specificity is one of the most important properties of carbenes in their reactions. Alcohols are typically used to probe the reactive spin states of carbenes: O? H insertions are assumed to be characteristic of singlet states, whereas C? H insertions are typical for the triplets. Surprisingly, the experiments presented here suggest that the spin ground state of diphenylcarbene 1 switches from triplet to singlet if the carbene is allowed to interact with methanol. Carbene 1 and methanol form a strongly hydrogen‐bonded singlet ground state complex that was synthesized in low‐temperature matrices and characterized by IR spectroscopy. This methanol complex is only metastable, and even at 3 K slowly rearranges to form the product of O? H insertion through quantum chemical tunneling. Thus, the ground state triplet (in the gas phase) carbene 1 forms exclusively the products expected from a singlet carbene. Whereas the assumption of spin specific reactions of carbenes is correct, the spin state itself can be changed by solvent interactions, and therefore widely accepted conclusions drawn from earlier experiments have to be revisited.     

Ab initio study of low-lying triplet states of the lithium dimer

Observation of Bose-Einstein condensation in Li27 initiated the interest in the scattering length of two ground state lithium atoms when they approach each other as a radical pair triplet aSigmau+3 state. But some properties of this state are still unknown. In present work, a number of low-lying triplet states of lithium molecule are calculated by multi-configuration self-consistent field (MCSCF) and response techniques with account of spin-orbit coupling, spin-spin coupling and some other magnetic perturbations. The singlet-triplet transition probabilities to the ground state are also presented. Most results are connected with the weakly bound lowest triplet a3Sigmau+ state, whose radiative lifetime and spin-splitting are unknown so far in spite of its great importance in Bose-Einstein condensation. Calculations indicate that this state has a very small spin-splitting, lambdass=-0.01 cm-1, which is negligible in comparison with the line-width in experimental Fourier transform spectra published so far. Similar splitting is obtained for the upper state of the 1(3)Sigmag+--a3Sigmau+ transition. This is in agreement with experimental rovibronic analysis of the 1(3)Sigmag+--a3Sigmau+ band system in which the triplet structure was not resolved. The radiative lifetime of the a3Sigmau+ state is predicted to exceed 10 h.     

Effects of chain length and Au spin-orbit coupling on 3(pi pi*) emission from bridging Cn2- units: theoretical characterization of spin-forbidden radiative transitions in metal-capped one-dimensional carbon chains [H3PAu(C[triple bond]C)nAuPH3

Density functional theory and CASSCF calculations have been used to optimize the geometries of binuclear gold(I) complexes [H(3)PAu(C[triple bond]C)(n)AuPH(3)] (n=1-6) in their ground states and selected lowest energy (3)(pi pi*) excited states. Vertical excitation energies obtained by time-dependent density functional calculations for the spin-forbidden singlet-triplet transitions have exponential-decay size dependence. The predicted singlet-triplet splitting limit of [H(3)PAu(C[triple bond]C)(proportional/variant)AuPH(3)] is about 8317 cm(-1). Calculated singlet-triplet transition energies are in reasonable agreement with available experimental observations. The effect of the heavy atom Au spin-orbit coupling on the (3)(pi pi*) emission of these metal-capped one-dimensional carbon allotropes has been investigated by MRCI calculations. The contribution of the spin- and dipole-allowed singlet excited state to the spin-orbit-coupling wave function of the (3)(pi pi*) excited state makes the low-lying acetylenic triplet excited states become sufficiently allowed so as to appear in both electronic absorption and emission.     

Electronic stabilization of ground state triplet carbenes

Based on systematic ab initio (CCSD(T)/cc-pVDZ) studies of substituent effects, we present a concept for the construction of electronically stabilized triplet ground state carbenes with singlet-triplet energy separations (DeltaEST) exceeding that of methylene. Sterically demanding and conjugating substituents were excluded from the selection of model compounds under investigation, as these either destabilize both the singlet and the triplet states or delocalize unpaired spins away from the carbene carbon. Negative partial charges on the carbene center allow for the prediction of the electronic stabilization of substituted carbenes. To decrease carbene reactivity, we chose beta-substituents with strong polar bonds. Among them, highly electronegative elements such as fluorine and oxygen enlarge the DeltaEST value with respect to hydrogen, while chlorine does not due to p-orbital participation.     

Singlet-triplet energy separation of cyclobutylidene

Ab initio (MP2, CCSD(T)) and density functional theory (BLYP, B3LYP) calculations provide insight concerning novel aspects of structure and bonding in cyclobutylidene (1). Singlet cyclobutylidene ((1)1) adopts a bicyclobutane-like structure (C(s) symmetry) that includes a weak, transannular bonding interaction between the carbene carbon and the opposing CH(2) group. Conformational ring inversion in (1)1 occurs through a transition state of C(2)(v)() symmetry (TS(1)1) with an enthalpy barrier of approximately 3 kcal/mol. Stabilization afforded the singlet state by the transannular interaction appears to be largely offset by a loss of hyperconjugative stabilization from the adjacent C-H bonds. Triplet cyclobutylidene ((3)1) exhibits a C(2)(v)() structure and conventional bonding. The triplet state lies 5.9 kcal/mol above the singlet ground state at the CCSD(T)/TZP//CCSD(T)/DZP level of theory. The singlet-triplet energy gap of cyclobutylidene (-5.9 kcal/mol) lies between that of an acyclic analogue, dimethylcarbene (-1.6 kcal/mol), and a highly strained analogue, cyclopropylidene (-13.8 kcal/mol). The magnitude of the energy gap suggests that triplet cyclobutylidene ((3)1) will be thermally accessible under a variety of experimental conditions.     

On the reversible O2 binding of the Fe-porphyrin complex

Electronic mechanism of the reversible O(2) binding by heme was studied by using Density Functional Theory calculations. The ground state of oxyheme was calculated to be open singlet state [Fe(S =1/2) + O(2)(S = 1/2)]. The potential energy surface for singlet state is associative, while that for triplet state is dissociative. Because the ground state of the O(2)+ deoxyheme system is triplet in the dissociation limit [Fe(S = 2) + O(2)(S = 1)], the O(2) binding process requires relativistic spin-orbit interaction to accomplish the intersystem crossing from triplet to singlet states. Owing to the singlet-triplet crossing, the activation energies for both O(2) binding and dissociation become moderate, and hence reversible. We also found that the deviation of the Fe atom from the porphyrin plane is also important reaction coordinate for O(2) binding. The potential surface is associative/dissociative when the Fe atom locates in-plane/out-of-plane.     

A theoretical study on the low-lying excited states of 2,2':5',2'-terthiophene and 2,2':5',2':5',2'-quaterthiophene.

The nature and properties of the low-lying singlet and triplet valence excited states of 2,2':5',2'-terthiophene (terthiophene) and 2,2':5',2':5',2'-quaterthiophene (tetrathiophene) are discussed on the basis of high-level ab initio computations. The spectroscopic features determined experimentally for short alpha-oligothiophenes are rationalised on theoretical grounds. Special attention is devoted to the nonradiative decay process through intersystem crossing (ISC) from the singlet to the triplet manifold, which is known to be relatively less efficient in tetrathiophene. Along the geometry relaxation of the S1 state of terthiophene, the S1 and T2 states become degenerate, which leads to a favourable situation for the occurrence of ISC. The parallel process is expected to be less favoured in tetrathiophene because of the less efficient spin-orbit coupling and the increase of the S1-T2 energy gap.     

Computational and experimental studies of the effect of substituents on the singlet-triplet energy gap in phenyl(carbomethoxy)carbene

The effect of aromatic substitution on the singlet-triplet energy gap in substituted phenyl(carbomethoxy)carbene (X-Ph-C-CO(2)CH(3), PCC) has been explored by time-resolved infrared (TRIR) spectroscopy and gas-phase computational methods. The ground state of para-substituted PCC is calculated to change from the triplet state in p-NO(2)-PCC (Delta G(ST) = 6.1 kcal/mol) to the singlet state in p-NH(2)-PCC (Delta G(ST) = -2.8 kcal/mol). The absence of solvent perturbation in the TRIR spectra of p-N(CH(3))(2)-PCC (which should have electronic properties similar to p-NH(2)-PCC) and parent PCC is consistent with their ground states lying > +/-2 kcal/mol from the next available electronic state, in line with the computational results. The observation of solvent perturbation in the TRIR spectra of p-OCH(3)-PCC and p-CH(3)-PCC implies that their ground states lie < +/-1 kcal/mol from their next available electronic state. This is in agreement with our computational results, which predict a gas-phase Delta G(ST) of -0.8 and 1.6 kcal/mol for p-OCH(3)-PCC and p-CH(3)-PCC as compared to Delta G(ST) values of -3.9 and -1.3 kcal/mol from polarizable continuum model (PCM) calculations with acetonitrile as a solvent. Gas-phase computational results for the meta- and ortho-substituted PCC species are also presented, along with selected linear free energy (LFE) relationships for the para and meta species.