C O M M U N I C A T I O N S
Table 1. The Photophysical Properties of o-HBDI and o-MBDI in
Various Solvents at Room Temperature
o-HBDI
o-MBDI
a
a
3
a
a
4
λabs
λem
Φf ×10-
τb
λabs
λem
Φf ×10-
τb
C6H12
CH2Cl2
CH3CN
H2O (pH ) 7)
385 605
386 603
383 602
380 495
600
3.1
2.2
1.5
0.9c
32.0 372 425
16.0 374 435
7.9 374 435
0.9 375 460
3.2
5.0
3.1
2.6
0.9
4.0
2.4
2.2
0.7
H2O (pH ) 12) 445 580
1.0
12.7
a Unit: nm. b Unit: ps. c Sum of the dual emission.
Figure 2. The absorption and emission spectra of o-HBDI in cyclohexane
(black solid line) and solid film (red solid line, emission only) and o-MBDI
(blue solid line) in cyclohexane.
resolved (see SI). The result in water can plausibly be rationalized
by the partial rupture of the intramolecular hydrogen bond,10
resulting in the prohibition of ESIPT. This viewpoint can be
supported by the lack of correlation between the finite decay of
normal emission (0.9 ps, Table 1) and system response limited-
rise dynamics of the tautomer (<150 fs). In pH ) 12, the o-HBDI
anion exhibits absorption and emission at 445 and 580 nm,
respectively. Comparing the anionic species, the red shift of the
zwitterionic emission can be rationalized by the reduction of
electron donating strength at the protonated N(2) nitrogen, resulting
in a decrease of the LUMO energy.
To sum up, we have synthesized a structural isomer of the core
chromophore (p-HBDI) in GFP. o-HBDI possesses a seven-
membered-ring hydrogen bond, from which ultrafast ESIPT takes
place, resulting in a proton-transfer tautomer emission of ∼605 nm
in nonpolar solvents. Although the bioactivity of o-HBDI is pending
further exploration, its future chemical derivation is versatile. It is
believed that fine tuning the proton-transfer emission can be
achieved via the derivation at the C(1) position, while the
radiationless quenching process may be further reduced by anchor-
ing bulky groups at the C(4) position, generating a new series of
isomers of p-HBDI with remarkable ESIPT properties.
Accordingly, the ∼605 nm emission in o-HBDI with an anoma-
lously large Stokes shift (peak-to-peak) of ∼10000 cm-1 relative
to the S0 f S1 absorption, is unambiguously ascribed to a tautomer
emission resulting from the ESIPT reaction, most probably via the
phenolic proton to the N(2) nitrogen, forming a zwitterionic species
(see TOC for structure). With a femtosecond fluorescence up-
conversion technique, the population decay of the 605-nm emission
band was measured to be 32 ( 0.2 ps, while the corresponding
rise time was beyond the system response of 150 fs, which consists
with the system response limited decay time monitored at 450 nm,
presumed to be the origin of normal emission.
To further gain insights into the ESIPT kinetics, the H-deuterated
O-D compound of o-HBDI, o-dBDI, was also prepared (see
Supporting Information) and investigated. Under the same experi-
mental condition as that performed for o-HBDI, the up-converted
tautomer emission in o-dBDI also revealed a system response
limited rise time and a population decay of 33 ( 0.3 ps. The results
demonstrate that the rate of ESIPT is quite insensitive to an H/D
exchange and point to an essentially barrierless potential energy
surface along the ESIPT reaction. Further support was also given
by the theoretical approach. Based on the time dependent DFT
method (TDDFT/B3LYP/cc-pVDZ and aug-cc-pVDZ) implemented
in the TURBOMOLE 5.8 software package9 (see SI), the ESIPT
process was calculated to be thermally favorable by ∼7.8 kcal/
mol (see TOC). Moreover, upon Franck-Condon excitation and
execution of the geometry relaxation, the TDDFT method could
not locate the energy minimum of the excited normal species, a
result which is consistent with a barrierless ESIPT process
concluded experimentally.
Supporting Information Available: Details for experimental
procedures, spectroscopic data, and X-ray studies. This material is
References
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As compared to those generally observed weak emissions for
p-HBDI (Φf ≈10-4 and τf ≈ 1.7 ps in toluene) at room temperature,4d
the tautomer emission yield of 3.1 × 10-3 with τf ≈ 32 ps in
cyclohexane implies that the hydrogen-bonding strength may, in
part, hinder the exocyclic C-C bonds rotation. Further support is
rendered by the much weaker normal emission (Φf ≈ 5 × 10-4
and τf ≈ 4 ps in cyclohexane, see Table 1) in o-MBDI that lacks
the seven-hydrogen bond formation. Nevertheless, the somewhat
weak proton-transfer tautomer emission may indicate the active
operation of the conformational relaxation owing to the loose
rigidity of the seven-membered-ring hydrogen bond. Note that
ESIPT still takes place in the solid film (vapor deposition onto a
quartz plate) of o-HBDI (Figure 2), resulting in a ∼595 nm tautomer
emission with Φf as high as 0.4 (τf ≈ 1.7 ns).
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As listed in Table 1, similar ultrasfast ESIPT was also observed,
giving a unique tautomer emission, in all aprotic solvents. However,
in protic solvent such as water (pH ) 7), dual emission, consisting
of normal (∼495 nm) and tautomer (∼600 nm) emission, was
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