Photoinduced Heterocyclic Ring-Opening of Furfural: Distinct Open-Chain Product

Identification by Ultrafast X-ray Transient Absorption Spectroscopy

Aditi Bhattacherjee,1,2,5 Kirsten Schnorr,1,2,6 Sven Oesterling,3 Zheyue Yang,1,2 Tian Xue,1,2 Regina de

Vivie-Riedle,3 and Stephen R. Leone*1,2,4

1
Department of Chemistry, University of California, Berkeley, California 94720, USA
2
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720,
USA
3
Department of Chemistry, Ludwig-Maximilians-Universität München, München 81377, Germany
4
Department of Physics, University of California, Berkeley, California 94720, USA

*Address for correspondence:

Prof. Stephen R. Leone

E-mail: srl@berkeley.edu

Telephone: (510)-643-5467, Fax: (510)-643-1376

Present address:
5
School of Chemistry, University of Bristol, Bristol BS8 1TH, United Kingdom
6
Paul Scherrer Institute, 5232 Villigen, Switzerland

S1
Figure S1: Cross-correlation trace of the 266 nm pump and X-ray probe pulses by measuring the
change in absorbance of the 2p
/ 3d core-excited Rydberg state of argon as a function of time delay.
The full-width-at-half-maximum (90 fs) of the cross-correlation defines the instrument response
function of the apparatus and the time delay at which it peaks defines time zero. Error bars denote a
95% confidence limit.

Figure S2: Comparison of the NEXAFS spectra of furfural (solid black line with error bars) with
those computed at the TDDFT level using (a) PBE0 / 6-311++G** and (b) CAM-B3LYP / 6-
311++G**. The color coding of the sticks is in accordance with the atom numbering scheme
introduced in Figure 2. The filled-in gray spectra represent convolutions of the theoretical stick
spectra with Gaussian functions having widths equivalent to the spectrometer resolution.

S2
Figure S3: Calculated (TDDFT) NEXAFS spectra of the cis and trans conformers of furfural.
Although the measurements cannot distinguish between these two conformers, other investigations
have established a ~1:4 cis:trans population ratio in the gas phase.1

S3
Estimation of percentage excitation and verification of linear regime of excitation

Typical 266 nm pulse energies and focusing conditions used in the experiment result in a

pump fluence of ~9 mJ/cm2 and peak intensities of ~1.2×1011 W cm-2 at the focus. The percentage of

molecules excited in the pump focus is estimated to be approximately 23%, based on the 266-nm

absorption cross-section of furfural (~2×1018 molecules cm-2) and the pump fluence. Errors in the

measured pulse energies or beam waist can alter the best estimate of the percentage excitation by

±5%; however, this uncertainty only affects the overall peak-amplitudes but not the relative

amplitudes or peak positions or even the extracted exponential time-constants from lineouts of the

measured differential absorbance. Most importantly, pump-power‒dependence measurements are

carried out to ensure that the experiment is performed in the linear regime of excitation and is devoid

of any multiphoton effects (Figure S4). All transient absorption measurements were carried out at a

pump fluence of ~9 mJ/cm2, in the vicinity of the first measured data-point shown in Figure S4.

Figure S4: 266 nm-power dependence of the amplitudes of peaks 7 (287.5 eV). Error bars denote a
95% confidence limit. Linear fitting gives a slope of 1.0±0.3 (error bar denotes one-standard error in
the least-squares fitting).

S4
Figure S5: X-ray transient absorption spectra of furfural measured at different pump-probe time-
delays between the 266 nm (pump) and soft X-ray (probe) beams (Colors progress from violet to
red with increasing time-delays from top to bottom, incrementing to the right). Each spectrum
represents the average differential absorption over the respective time-window. The black
baseline in each window is measured at negative time-delays (probe arriving earlier than the
pump). Error bars denote a 95% confidence limit over 24 measured spectra.

S5
Figure S6: “Pump-on X-ray absorption spectra” (i.e. of photoexcited molecules only), derived from
the transient absorption spectra shown in Figure S5 and assuming a ~23% photoexcitation, same
pattern of time delays as Figure S5. Error bars denote a 95% confidence limit over 24 measured
spectra. The solid black line in each window is derived from the transient spectrum measured at
negative time-delays and is representative of the ground-state NEXAFS of furfural.

S6
Figure S7: Temporal evolution of P1, P2, P6, and P7 up to 10 ps. Inset shows the exponential time-
constants for all the peaks, when fitted to an exponential rise (P2, P6, P7) or decay (P1), convolved
with a (90 fs) Gaussian instrument response function (IRF).

S7
Figure S8: Simulated NEXAFS spectra for the (a) C(α)-O ring opening conical intersection (b) C(δ)-
O ring opening conical intersection (c) ring-puckering conical intersection (d) conical intersection
involving the non-bonding orbital (N) of the carbonyl oxygen shown as convolutions of the
underlying stick spectra (same atom numbering scheme as Figure 2). An energy cut-off at 288 eV is
applied. The structures of the various conical intersections are obtained from reference 17 (main text).

S8
Figure S9: Comparisons of the measured differential X-ray absorption spectra (colored lines
connecting the measured datapoints) with the computed differential spectra (black traces); a
horizontal dashed gray line provides a reference for the zero baseline. Blue, green and red lines
correspond to the experimental spectra measured between (a) -80 to 20 fs, (b) 120 to 200 fs, and (c)
6.5 to 10 ps. The black curves in each panel correspond to 23% scaled subtractions of the computed
ground state (S0) X-ray spectrum of furfural from the (a) computed S2 (FC), (b) computed CIO (solid
black) and CIP (dotted black), and (c) computed ring-opened (RO) carbene X-ray spectra. (Note the
drop-off in the black trace below the baseline in all three panels for energies above 288 eV is an
artifact due to the theoretical energy cut-off imposed for the corresponding excited states and carbene
species).

S9
Figure S10: Calculated X-ray absorption spectra of an open-shell biradical populated in a few
trajectories in the ring-opening reaction of furfural. The first pre-edge transition in the open-shell
biradical is a core-to-2p (SOMO) resonance, similar in energy to the core-to-2p (LUMO) resonance in
the open-shell carbene. However, the biradical structure, unlike the carbene, does not correspond to a
stationary point.

A note on photochemical ring-opened reaction products and isomers

The general consensus regarding ring-opening in furan is that it involves either a carbene

intermediate (α- or β-carbenes formed via 1,2- or 2,1-hydrogen atom migrations)2-4 or a biradical

intermediate (via a homolytic C-O bond fission).5-6 These intermediates, notably proposed in pyrolysis

studies, undergo facile electronic rearrangements and pyrolyze to secondary decomposition products.

Pyrolysis experiments usually involve various levels of seeding in buffer gas mixtures with residence

times of several tens to hundreds of microseconds in the reactor or shock tube, and they reveal both

temperature- and pressure-dependent rate constants.7 The results of these thermal, ground-state

reactions are therefore not directly comparable to femtosecond time-resolved measurements of

photochemical reactions, which involve excited electronic states and give insights into the very early

stages of the dissociation. Comparisons between the results of photochemical and pyrolysis

experiments are mainly valid for ground state photochemistry alone, specifically, when photoexcited

molecules return to the ground state via internal conversion and subsequently dissociate.

S10
Photochemical ground-state reactions may be considered as the equivalent of thermal decomposition

under collision-free conditions.8

Initial propositions of the initiation of furan pyrolysis by a C-O bond scission5 were later

ruled out by ab initio calculations,9 which revealed too high a ring-scission barrier to account for the

observed rate of decomposition. The same work showed that the formation of carbenes allowed the

kinetics of furan pyrolysis to be satisfactorily modelled. Formation of a carbene intermediate is

computed to have a lower activation barrier than that of a biradical.10 1,3-Diradical (with the unpaired

electron localized on different carbon atoms) resonance structures are obtained as stationary points in

quantum dynamical studies of furan, indicating that the chemistry is both rich and complex.11 Time-

dependent density functional theory (TDDFT) calculations of furan and thiophene also show the

significance of diradical electron distributions.12-13 High-level, multiconfiguration self-consistent field

calculations have recently revealed biradical character of the ring-opened conical intersection (CIO),

with a radical centered on the oxygen atom and also in the photoproduct. The X-ray spectrum of the

photoproduct simulated at the oxygen K-edge shows a red-shift of 3 to 4 eV in the near-edge

transition compared to the molecular ground-state.14 TDDFT molecular dynamics simulations of

relaxation dynamics in furan additionally show two possible (minor) channels involving ring-opening

- isomerization to stable, closed-shell photoproducts (2,3-butadienal and cyclopropen-3-carbaldehyde)

in the ground state.15

In furfural, we find that the carbene is the global minimum structure for the ring-opened form.

A biradical isomer (Figure S10), although transiently populated in a few trajectories, is not obtained

as a minimum energy structure. CASSCF calculations with slightly different active spaces for the two

isomers show that the biradical lies approximately 2 eV higher in energy in comparison to the

carbene. The computed X-ray spectra for both isomers, however, are very similar at the carbon K-

edge as both contain a core electronic transition into a non-bonding 2p orbital (Figures 3 and S10).

Complementary experiments at the oxygen K-edge (~543 eV) can be used to investigate the

significance of a biradical intermediate containing an unpaired electron localized on the oxygen atom.

In particular, the emergence of a red-shifted 1s(O)→n(O) transition with respect to a 1s(O)→π*

ground-state transition will be evidence for ring-opening via a biradical generated through C-O bond

S11
fission.14 It is possible that biradical structures have a minor influence on the ring-opening pathway in

furfural. Nonetheless, the NEXAFS signature of a 2p non-bonding orbital at the carbon K-edge is

direct proof that ring-opening occurs in furfural.

Closed-shell molecules, such as those computationally investigated for furan,15 are also

considered as alternative, stable photoproducts for ring-opening in furfural. These molecules (penta-

2,3-diene-1,5-dial and cyclopropene-1,3-dicarbaldehyde) may be formed via H atom migrations and

resultant isomerizations of the carbene. It must be noted that the first computed near-edge transition in

these molecules is 1s→π* (LUMO), which typically lies above 284.5 eV.16 Significant spectral

overlap is expected to occur in the computed NEXAFS peaks above 284 eV for the open- and closed-

shell photoproducts. This precludes estimations of the specific contributions of H-atom migrations

and related isomerizations to the experimental NEXAFS spectra measured at long time delays.

However, it must be emphasized that the ultrafast carbene formation is the primary photochemical

pathway and ensuing isomerizations are expected to be secondary processes occurring on longer

timescales. The results of the femtosecond X-ray transient absorption experiments outlined here

enable the identification of the ultrafast, primary photochemical ring-opening step.

Figure S11: Temporal evolution of the integrated differential absorbance of P6 over a 1-eV spectral
window between 286 eV and 287 eV. Blue squares correspond to the integrated areas at different
pump-probe time delays. The solid black line is an exponential rise of the depletion, convolved with a
Gaussian IRF of fixed width (90 fs). An 8% standard error is obtained for the mean integrated area in
the plateau of the depletion (i.e. for time delays ≥ 350 fs)

S12
Figure S12: Fits of the near-edge peaks P4 (green) and P6 (cyan) of ground-state NEXAFS of
furfural to Gaussian functions yield a width of 0.95 eV for P6. Black squares denote experimentally
measured datapoints and the solid blue line is the convolution of the two Gaussian functions for the
overall fit. A rising edge due to core ionization (not shown) is also included for the fitting of the
experimental data over 288 eV.

Figure S13: Deconvolution procedure of the scaled-down (factor of 3.5) P2 rise (orange) from P1
decay (green) to eliminate the contribution from the low-energy wing of P2 in the long-delay limit. A
similar procedure was applied for characterizing the time-constants of the evolving core-valence
resonances in the A-band photodissociation of methyl iodide17 and allyl iodide18, where one of the
observed transient peaks had a spectral overlap with the product I* absorbance.

S13
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