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Physical Chemistry Chemical Physics Accepted Manuscript

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
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Dithiafulvene derivatized donor-acceptor norbornadienes with
redshifted absorption
Mads Mansø,a,b Martin Drøhse Kilde,a Sandeep Kumar Singh, b Paul Erhart,b Kasper Moth-Poulsenb
and Mogens Brøndsted Nielsena,*
Photoisomerization of norbornadiene (N) to its metastable isomer quadricyclane (Q) has attracted interest as a strategy
for harvesting and storing solar energy. For this strategy to mature the absorption maximum of the N has to be moved
from the UV to visible region. Here we show that functionalization of the system with dithiafulvene (DTF) electron donors

causes remarkabe redshifts of various N derivatives. Thus, some derivatives were found to absorb light with an absorption
onset up to 556 nm. The incorporation of DTF units come, however, with a drawback in regard to achieving reversible N-
to-Q and Q-to-N isomerizations. For some derivatives, the photoisomerization was completely quenched. The compounds
were subjected to a computational study to shed light on the underlying reason for this reluctance to undergo
photoisomerization. The computational study revealed that in these systems, the first excited state (S1) is positioned close
to or lower than the transition state for photoconversion, effectively blocking a possible conversion to Q, thus revealing a
practical challenge for future design of N-Q energy storage systems with improved solar spectrum match.

attaching a DTF unit to the norbornadiene arose. Here we

Introduction present the synthesis and characterization of several DTF
functionalized donor-acceptor norbornadienes, all with a
Due to the increasing energy demand, new more sustainable
cyano group as the acceptor unit.
solutions have to be developed. One such solution is reversible
harvesting and storage of solar energy in chemical bonds so-
called molecular solar thermal systems (MOST).1-4 In this
regard, one molecular system is the norbornadiene (N) -
quadricyclane (Q) photoswitch owing to the large energy
difference between the two isomers.4,5 A challenge with this
photoswitch is, however, a lack of solar spectrum match due
to the absorption of N in the UV region. To address this issue,
functionalization of the photoswitch to obtain a redshifted
absorption is investigated.6,7 One strategy is incorporation of
donor and acceptor groups at one of the double bonds, which
has previously been shown to redshift the absorption to closer
match the solar spectrum while keeping the molecular weight
low.8-10 Tetrathiafulvalene (TTF) and its half unit dithiafulvene
(DTF) (Figure 1) are good electron donors due to their low
oxidation potentials.11 Earlier some of us have placed a DTF12
or TTF13 unit in conjugation with the dihydroazulene (DHA)
Figure 1: Structures of the norbornadiene/quadricyclane (N/Q) couple, dithiafulvene
photoswitch (Figure 1), and in both cases a significant redshift
(DTF), tetrathiafulvalene (TTF) and DTF (DTF-DHA) and TTF (TTF-DHA) substituted
in the DHA absorption was seen. Therefore, our interest in dihydroazulenes (DHAs).

Results and discussion

a. Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-
2100 Copenhagen Ø. E-mail: mbn@chem.ku.dk
b. Department of Chemistry and Chemical Engineering, Chalmers University of
c. Technology, Kemivägen 10, 412 96 Gothenburg, Sweden
Synthesis. Our first objective was to prepare acetylenic DTF building
†Electronic Supplementary Information (ESI) available: NMR spectra, switching blocks that can be coupled to the N core, starting from the three
studies, and calculational details. See DOI: 10.1039/x0xx00000x acetylenic carbonyls 114, 215 and 316 (Scheme 1) all prepared from

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literature procedures. The aldehyde 1 was reacted in a Horner- View Article Online
Wadsworth-Emmons reaction with the known phosphonate ester DOI: 10.1039/C8CP07744D
417 using sodium hexamethyldisilazide (NaHMDS) as base to give
the DTF functionalized trimethylsilyl (TMS) end-capped alkyne 5.
Compound 6 incorporating two TMS protected alkynes was

Physical Chemistry Chemical Physics Accepted Manuscript

prepared in a similar way from 2 and the phosphonate ester 718. To
further investigate the role of the DTF unit, an analogue with the
DTF placed one phenylene unit further away from the
norbornadiene unit was synthesized in a Wittig reaction between 3
and the known phosphonium tetrafluoroborate salt 819, using
triethylamine as base, furnishing the product 9.
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Scheme 1: Synthesis of the DTF functionalized acetylenes 5, 6 and 9. Conditions: i)

NaHMDS, THF, -78 oC to rt; ii) Et3N, THF/MeCN, rt.

The TMS protected acetylene 5 was then deprotected with

potassium carbonate in MeOH/THF, and the resulting terminal
alkyne was thereafter directly employed in a Sonogashira
coupling with the known 2-chloro-3-cyanonorbornadiene10 to
afford the DTF-N 10 in a yield of 66% (Scheme 2). The same Scheme 2: Synthesis of the DTF-functionalized norbornadienes 10, 11, 12 and 13.
conditions were applied in the case of 9, giving DTF-N 11 in Conditions: i) 1) K2CO3, MeOH/THF; 2) 2-chloro-3-cyanonorbornadiene, Pd(PPh3)2Cl2,
64% yield. Similarly, 6 was converted into the N-DTF-N product CuI, THF/Et3N.

12 in a yield of 54%. Also, some of the by-product 13 (N-DTF-

Spectroscopy and photoconversion studies. The four synthesized
DTF-N) was isolated in this reaction, the properties of which
norbornadienes 10-13 were subjected to UV-Vis absorption
were also studied (vide infra). The dimers were isolated as
spectroscopy studies. The spectra (Figure 2) reveal that all four
mixtures of diastereoisomers.
compounds have significantly redshifted longest-wavelength
absorption maxima relative to the parent norbornadiene (N) and
absorption onsets at or beyond 500 nm (Table 1), while the onset of
N is at 267 nm.

Table 1: Absorption maxima and onsets for the DTF-norbornadienes and the
unsubstituted norbornadiene.

Compound max Aonseta

DTF-N 10 441 nm 509 nm
DTF-N 11 397 nm 499 nm
N-DTF-N 12 475 nm 556 nm
N-DTF-DTF-N 13 470 nm 548 nm
N <200 nm 267 nm
a) Aonset is defined as the wavelength where the absorbance is 10-3 (based on
normalized absorption spectrum).

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Figure 2: UV-Vis absorption spectra of DTF norbornadienes. Green: 10, Red: 11, Blue:
12, Black: 13.
First, photoconversion studies were performed of the DTF-N
10 (Figure 3). Upon irradiation at 440 nm, gradual switching to
the corresponding quadricyclane (DTF-Q) was observed with
an isosbestic point, but for the thermal Q-to-N back-reaction
(conducted at either 25 °C or 50 °C), no isosbestic points were
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observed, which is most likely due to degradation (Figure 3).
Figure 3: Top: Spectral evolution upon photoisomerization of 10 by irradiation at 440
nm for 8 h (in toluene). Bottom: Spectral evolution for the corresponding back-reaction
performed at 50 °C.
Irradiation of DTF-N 11 at 397 nm showed more promising
results with isosbestic points in both directions and with a
thermal Q-to-N back-reaction half-life of 378 minutes in
toluene (Figure 4). But for this system an equally slow N-to-Q
photoisomerization reaction was observed as for 10, and full
isomerization required continuous irradiation for 8 hours. To
further investigate the photoisomerization, an NMR scale
experiment was performed, but irradiation with a high
powered LED at 405 nm for 14 hours showed no isomerization
of the norbornadiene form, only minor degradation, possibly
due to the higher concentration causing inner filter effects
along with a low quantum yield (see ESI). We cannot say for
certainty which degradation products are formed, but
oxidative dimerization is known to occur for dithiafulvenes
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(dimerization of two radical cations),20 and an oxidation
View Articleof 11
Online
to its reactive radical cation is DOI: possibly promoted
10.1039/C8CP07744D
photochemically.
Physical Chemistry Chemical Physics Accepted Manuscript
Figure 4: Top: Spectral evolution upon photoisomerization of 11 by irradiation at 397
nm in toluene. Bottom: Spectral evolution for the corresponding back-reaction
performed at 25 °C in toluene.
Photoisomerization experiments were next performed on the
two norbornadiene dimers 12 (N-DTF-N) and 13 (N-DTF-DTF-
N). Yet, no change in the UV-Vis spectrum by irradiation at
340, 357, 429 and 474 nm was observed for 12, and no change
was observed for 13 upon irradiation at 341, 408 and 474 nm.
Irradiations were also performed at lower temperatures (-20, -
40 and -60 °C) for both compounds, but again no changes in
the UV-Vis absorption spectra were observed.
Computational studies. To rationalize the experimental
results, we note that in order for a photoswitch to work, one
requires the S1 energy for the initial state to be higher than for
the transition state (TS).21 To explore this aspect, we mapped
out ground and excited energy landscapes using static and
time dependent density functional theory calculations (see
Computational method section for details). The results (Figure
5) show that compounds 10 and 11 fulfill the basic energy
condition formulated above, irrespective of the functional
employed for the calculation (B3LYP or CAM-B3LYP). This is
consistent with the experimental observation that both of
these two compounds can be switched (even if compound 10
decomposes in the process).
For norbornadiene dimers 12 and 13 the situation is more
involved. Whereas the energy condition is fulfilled for the first
isomerization step (NN->NQ), the S1 energy of the
intermediate configuration (NQ) is well below the energy of
the second TS (NQ->NN). At the same time, the lowest
absorption energy for NQ is similar to NN. This suggests that
one of the two N units in 12 and 13 can be switched (NN->NQ).
Yet photoabsorption of the intermediate configuration (NQ),
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which occurs at a similar wavelength as for the initial state
(NN), creates an excited state that cannot overcome the
barrier to the fully switched configuration (NQ->QQ) and
rather relaxes by back-conversion to the initial state (NQ->NN).
This provides a simple rationale for the failure to switch these
compounds in experimental settings.
It is furthermore instructive to put the present results in
relation to other molecules with multiple N units.22,23
Compared to the compounds from the latter study with a
phenylene spacer (onset ≤ 411 nm) the present molecules
exhibit an energetically much lower onset of absorption; 12:
onset = 556 nm, 13: onset = 548 nm (see Table 1). The entire S1
landscape should thus be shifted notably downward, which
pushes the S1 energy for the intermediate NQ configurations
below the TS for the NQ->NN conversion. The redshift in these
systems is thus effectively too strong to render molecules that
are functional for MOST applications.
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Figure 5: S0 and S1 energy landscape between NN and QQ for compounds 10
(a), 11 (b), 12 (c), and 13 (d) from TDDFT using B3LYP and CAM-B3LYP.
Conclusions
In conclusion, a selection of dithiafulvene-functionalized
norbornadiene derivatives was prepared using the
Sonogashira coupling reaction in the key step where the units
are linked together. These derivatives containing either one or
two norbornadiene units have significantly redshifted longest-
wavelength absorption maxima relative to the parent
norbornadiene compound. The dithiafulvene unit has,
however, an unfortunate influence on the ability of these
compounds to undergo photoisomerization. To obtain
photoisomerization, we found that the dithiafulvene and
norbornadiene units had to be separated by a phenylene
spacer. The reluctance of some of the compounds to undergo
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photoswitching was rationalized in a computational Viewstudy. For
Article Online
the compounds containing two norbornadiene units, the
DOI: 10.1039/C8CP07744D
transition state on the ground state energy surface between
NQ and QQ was found to be of higher energy than the energy
of first excited state. This prevents the second
Physical Chemistry Chemical Physics Accepted Manuscript
photoisomerization. If the first photoisomerization to QC does
in fact occur, this isomer is likely returning to the original NN in
an ultrafast reaction, which could explain that no isomerization
was observed experimentally even at low temperatures. The
work shows the challenges in designing compounds with
adequate spectral behaviour and switching properties. One
compound stood out, however, the DTF-phenylene-N
compound 11, exhibiting a remarkable absorption redshift and
maintaining reversible N-Q switching behaviour.
Experimental section
Synthesis. 114, 215, 316, 417, 718, 819 and 2-chloro-3-
cyanonorbornadiene10 were synthesized according to
literature procedures. THF was distilled freshly from
Na/benzophenone. NMR spectroscopy was performed on a
Bruker instrument with a non-inverse cryoprobe at 500 MHz
(1H) or 126 MHz (13C) using the residual solvent peak as the
reference (CDCl3: δH = 7.26 ppm and δC = 77.16 ppm). CDCl3
was purchased unstabilized and passed through activated
basic alumina prior to use. HRMS was recorded on an ESP-
MALDI-FT-ICR spectrometer equipped with a 7 T magnet
calibrated with NaTFA cluster ions. Flash column
chromatography was performed with silica of the particle size
40-63 µm. UV-Vis absorption spectra were recorded on a Cary
50 Bio. All UV-Vis absorption spectroscopy were performed
with argon-flushed solutions.
Compound 5: To a solution of 4 (405 mg, 1.33 mmol) in
anhydrous THF (10 mL) at -78 °C was added NaHMDS (2.4 mL,
0.6 M in toluene, 1.4 mmol), and the mixture was stirred for 1
h. The mixture was transferred via cannula to a solution of 1
(235 mg, 1.86 mmol) in anhydrous THF (10 mL) at -78 °C. The
reaction mixture was stirred for 1 h while reaching rt before it
was poured into water/brine (1:1, 150 mL) and extracted with
CH2Cl2 (3 x 50 mL). The combined organic phases were dried
over MgSO4, filtered and concentrated in vacuo. Flash column
chromatography (10% CH2Cl2/Petroleum spirit) gave 5 as a
slightly yellow oil (140 mg, 35%). 1H NMR (500 MHz, CDCl3): δ =
5.42 (s, 1H), 2.43 (s, 3H), 2.38 (s, 3H), 0.21 (s, 9H) ppm. 13C
NMR (126 MHz, CDCl3): δ = 148.98, 127.45, 126.65, 104.42,
102.31, 92.51, 19.09, 19.08, 0.24 ppm.
Compound 6: To a solution of 7 (308 mg, 326 μmol) in
anhydrous THF (10 mL) at -78 °C was added NaHMDS (0.6 M in
toluene, 1.55 mL, 930 μmol). The mixture was stirred for 1 h at
-78 °C before it was transferred via cannula to a solution of 2
(228 mg, 1.03 mmol) in anhydrous THF (10 mL) at -78 °C. The
mixture was stirred at -78 °C for 2.5 h before it was poured
into a saturated aqueous solution of ammonium chloride (100
mL) and extracted with CH2Cl2 (3 x 100 mL). The combined
organic phases were dried over Na2SO4, filtered and
concentrated in vacuo. Flash column chromatography (10%
CH2Cl2/Heptane) furnished 6 as a slightly yellow oil (212 mg,
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53%). TLC (10% CH2Cl2/Heptane): Rf = 0.33. 1H NMR (500 MHz,
CDCl3): δ = 2.87 (q, J = 7.3 Hz, 4H), 1.33 (t, J = 7.3 Hz, 6H), 0.22
(s, 18H) ppm. 13C NMR (126 MHz, CDCl3): δ = 158.05, 129.79,
103.10, 100.19, 87.46, 30.67, 15.10, 0.18 ppm. HR-MS (MALDI+
FT-ICR, dithranol): m/z = 428.06200 [M·+], calcd. for
[C18H28S4Si2+]: m/z = 428.06069.
Compound 9: To a solution of 3 (413 mg, 2.04 mmol) and 8
(2.03 g, 3.99 mmol) in anhydrous THF/MeCN (100 mL, 10:2)
was added Et3N (0.7 mL, 5.02 mmol) and the mixture was
stirred at rt for 20 h. The mixture was poured into brine/H2O
(100 mL, 1:1) and extracted with CH2Cl2 (4 x 100 mL). The
combined organic phases were dried over Na2SO4, filtered and
concentrated in vacuo. The crude mixture was purified by flash
column chromatography (60% CH2Cl2/Heptanes) yielding 9 as a
red solid (639 mg, 77%). 1H NMR (500 MHz, CDCl3): δ = 7.44 (d,
J = 8.3 Hz, 2H), 7.13 (d, J = 8.3 Hz, 2H), 6.42 (s, 1H), 3.86 (s, 3H),
3.85 (s, 3H), 0.25 (s, 9H) ppm. 13C NMR (126 MHz, CDCl3): δ =
160.26, 159.79, 135.79, 132.33, 131.71, 131.70, 129.47,
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126.61, 120.95, 114.86, 105.14, 95.27, 53.60, 53.46, 0.12 ppm.
HR-MS (ESI+ FT-ICR): m/z = 405.06596 [M+H+], calcd. for
[C19H21O4S2Si+]: m/z = 405.06450.
Compound 10: To a solution of 5 (60 mg, 197 μmol) in
THF/MeOH (10 mL, 1:1) was added K2CO3 (41 mg, 297 μmol)
and the mixture was stirred for 30 min at rt. The mixture was
poured into H2O (50 mL) and extracted with CH2Cl2 (3 x 30 mL).
The combined organic phases were dried over Na2SO4, filtered
and almost concentrated in vacuo. Et3N (20 mL) was added,
and the mixture was concentrated to approximately 10 mL.
THF (10 mL) and 2-chloro-3-cyanonorbornadiene (90 mg, 594
μmol) were added, and the mixture was argon-flushed.
Pd(PPh3)2Cl2 (10 mg, 14 μmol) and CuI (4 mg, 21 μmol) were
added, and the mixture was stirred for 3.5 h. H2O (100 mL) was
added before the mixture was extracted with CH2Cl2 (3 x 30
mL). The combined organic phases were dried over Na2SO4,
filtered and concentrated in vacuo. Flash column
chromatography (60% CH2Cl2/Heptane) furnished 10 as a dark
orange thick oil (45 mg, 66%). TLC (60% CH2Cl2/Heptanes): Rf =
0.31. 1H NMR (500 MHz, CDCl3): δ = 6.85 (dd, J = 5.0, 3.1 Hz,
1H), 6.80 (dd, J = 5.0, 3.1 Hz, 1H), 5.66 (s, 1H), 3.88–3.85 (m,
1H), 3.76–3.74 (m, 1H), 2.48 (s, 3H), 2.40 (s, 3H), 2.27 (dt, J =
7.0, 1.6 Hz, 1H), 2.18 (dt, J = 7.0, 1.6 Hz, 1H) ppm. 13C NMR
(126 MHz, CDCl3): δ = 153.64, 153.38, 142.40, 140.98, 129.85,
125.51, 124.59, 117.21, 106.43, 94.38, 90.98, 72.18, 57.04,
53.89, 19.15, 18.96 ppm. HR-MS (MALDI+ FT-ICR): m/z =
346.99295 [M·+], calcd. for [C16H13NS4+]: m/z = 346.99253.
Compound 11: To a solution of 9 (301 mg, 744 μmol) in
THF/MeOH (40 mL, 1:1) was added K2CO3 (402 mg, 2.91
mmol), and the mixture was stirred at rt for 20 min. The
mixture was passed through a plug of silica (40-63 μm, CH2Cl2)
and nearly concentrated in vacuo. Et3N (25 mL) was added,
and the mixture was concentrated to approximately 15 mL in
vacuo. Freshly distilled THF (15 mL) and 2-chloro-3-
cyanonorbornadiene (76 mg, 501 μmol) were added, and the
mixture was flushed with argon. Pd(PPh3)2Cl2 (56 mg, 80 μmol)
and CuI (15 mg, 79 μmol) were added, and the mixture was
stirred for 6 h. The mixture was poured into water (100 mL)
and extracted with CH2Cl2 (4 x 100 mL). The combined organic
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phases were dried over Na2SO4, filtered and concentrated in
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vacuo. Small amounts of 80% CH2Cl2/Heptane were added, and
DOI: 10.1039/C8CP07744D
the precipitate was filtered off. The filtrate was concentrated
and purified by flash column chromatography (80%
CH2Cl2/Heptane) furnishing 11 as an orange solid (144 mg,
Physical Chemistry Chemical Physics Accepted Manuscript
64%). M.p.: 120–122 °C. TLC (80% CH2Cl2/Heptanes): Rf = 0.36.
1H NMR (500 MHz, CDCl ): δ = 7.49 (d, J = 8.3 Hz, 2H), 7.19 (d, J
3
= 8.3 Hz, 2H), 6.88 (ddd, J = 5.1, 3.0, 0.7 Hz, 1H), 6.86 (ddd, J =
5.1, 3.0, 0.7 Hz, 1H), 6.45 (s, 1H), 3.91 – 3.89 (m, 1H), 3.87 (s,
3H), 3.86 (s, 3H), 3.87–3.84 (m, 1H), 2.32 (dt, J = 7.0, 1.7 Hz,
1H), 2.23 (dt, J = 7.0, 1.6 Hz, 1H) ppm. 13C NMR (126 MHz,
CDCl3): δ = 160.19, 159.69, 154.08, 142.27, 141.38, 136.85,
132.92, 132.32, 131.86, 129.50, 128.28, 126.82, 119.58,
116.55, 114.49, 108.07, 84.23, 72.85, 57.34, 54.21, 53.65,
53.51 ppm. HR-MS (ESI+ FT-ICR): m/z = 448.06965 [M·+], calcd.
for [C24H18NO4S2+]: m/z = 448.06718. EA (C24H17NO4S2): calcd. C
64.41, H 3.83, N 3.13; found C 64.25, H 3.92, N 3.24.
Compound 12: To a solution of 6 (54 mg, 0.13 mmol) in
THF/MeOH (10 mL, 1:1) was added K2CO3 (87 mg, 0.63 mmol),
and the mixture was stirred at rt for 45 min. The mixture was
poured into water (100 mL) and extracted with CH2Cl2 (3 x 30
mL). The combined organic phases were dried over MgSO4,
filtered and almost concentrated in vacuo, before Et3N (20 mL)
was added, and the mixture was concentrated to
approximately 10 mL. THF (10 mL) and 2-chloro-3-
cyanonorbornadiene (106 mg, 0.699 mmol) were added, and
the mixture was flushed with argon. Pd(PPh3)2Cl2 (9 mg, 13
μmol) and CuI (4 mg, 21 μmol) were added, and the mixture
was stirred for 22h at rt. The reaction mixture was poured into
H2O and extracted with CH2Cl2 (3 x 50 mL). The combined
organic phases were dried over MgSO4, filtered and
concentrated in vacuo. Flash column chromatography (70%
CH2Cl2/Heptane) followed by size exclusion chromatography
(SX3, CH2Cl2) gave 12 (35 mg, 54%) and 13 (9 mg, 18%). 12:
M.p.: 114–118 °C. TLC (70% CH2Cl2/Heptanes) = 0.47. 1H NMR
(500 MHz, CDCl3): δ = 6.87 (dd, J = 5.0, 3.0 Hz, 2H), 6.84–6.82
(m, 2H), 3.91–3.85 (m, 2H), 3.87–3.81 (m, 2H), 2.93 (q, J = 7.3
Hz, 4H), 2.29 (dt, J = 7.0, 1.7 Hz, 2H), 2.20 (dt, J = 7.0, 1.6 Hz,
2H), 1.33 (t, J = 7.3 Hz, 6H) ppm. 13C NMR (126 MHz, CDCl3): δ =
164.82, 164.81, 153.13, 142.36, 141.17, 131.02, 126.13,
117.01, 103.33, 92.51, 85.00, 72.47, 72.46, 56.97, 54.10, 30.74,
15.15. ppm. (The two peaks at 72.47 and 72.46, as well as the
two peaks at 164.82 and 164.81 split up due to
diastereoisomers.) HR-MS (MALDI+ FT-ICR): m/z = 514.06586
[M·+], calcd. for [C28H22N2S4+]: m/z = 514.06603. 13: TLC (70%
CH2Cl2/Heptanes) = 0.53. 1H NMR (400 MHz, CDCl3): δ = 6.87
(dd, J = 5.1, 3.0 Hz, 1H), 6.82 (dd, J = 5.1, 3.1 Hz, 1H), 3.89 –
3.87 (m, 1H), 3.83 – 3.80 (m, 1H), 2.94 (q, J = 7.3 Hz, 2H), 2.90
(q, J = 7.3 Hz, 2H), 2.29 (dt, J = 7.1, 1.6 Hz, 1H), 2.20 (dt, J = 7.1,
1.6 Hz, 1H), 1.34 (br. t, J = 7.3 Hz, 6H) ppm. 13C NMR (126
MHz): δ = 164.23, 153.10, 142.38, 141.15, 132.76, 128.81,
126.23, 117.01, 103.45, 93.15, 84.88, 82.21, 80.87, 72.45,
56.93, 54.09, 30.90, 30.67, 15.20, 15.10 ppm. HR-MS (MALDI+
FT-ICR): m/z = 796.03283 [M·+], calcd. for [C40H32N2S8+]: m/z =
796.03257.
J. Name., 2013, 00, 1-3 | 5
 PleaseChemistry
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Chemical Physics
ARTICLE
Computational methods. Molecular geometries (on the S0
landscape) were optimized at the density functional theory
(DFT) level. Optical properties and the excited (S1) energy
landscape were evaluated using time dependent density
functional theory (TDDFT) at fixed geometries. These
calculations were carried out using the B3LYP24 and CAM-
B3LYP25 functionals as implemented in the NWChem code26 in
combination with a 6-311G* basis set27,28. This computational
setup was previously benchmarked for related systems29 and
employed in related studies.30 Both B3LYP and CAM-B3LYP
systematically underestimate the experimental absorption
energies (Table S1), a behavior that is well-known for these
functionals.26 Apart from this redshift, they are, however, in
qualitative agreement with the experimental data.
Transition states between N and Q (monomeric compounds
10, 11) as well as between NN and NQ and between NQ and
QQ (dimeric compounds 12, 13) were determined using the
Published on 10 January 2019. Downloaded on 1/21/2019 2:21:01 AM.
nudged elastic band method while the biradical character of
the transition state was modeled using broken-symmetry
unrestricted DFT calculations.31,32 S0 energies were then
obtained by evaluation of the ground state energy using DFT
for the initial, final, and transition states. The corresponding S1
energies were subsequently determined by adding the first
excitation energy from TDDFT calculations at fixed molecular
geometry.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
University of Copenhagen is acknowledged for financial
support.
Notes and references
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 Page 7 of 7 Physical Chemistry Chemical Physics

Table of contents entry View Article Online

DOI: 10.1039/C8CP07744D

Physical Chemistry Chemical Physics Accepted Manuscript

Norbornadiene monomers and dimers incorporating an electron-donating
dithiafulvene unit were prepared and studied for their absorption properties and
photoswitching abilities.
Published on 10 January 2019. Downloaded on 1/21/2019 2:21:01 AM.