D 3 NJ 00570 D

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Dual emission of ESIPT-capable

2-(2-hydroxyphenyl)-4-(1H-pyrazol-1-yl)
Cite this: New J. Chem., 2023,
47, 6361 pyrimidines: interplay of fluorescence and
phosphorescence†
Nikita A. Shekhovtsov, *a Elena B. Nikolaenkova,b Alexey A. Ryadun,a
Sofia N. Vorobyeva,a Viktor P. Krivopalovb and Mark B. Bushuev *a
ESIPT-capable pyrimidine-based compounds featuring short O–H N intramolecular hydrogen bonds,

2-(2-hydroxyphenyl)-4-(3,5-dimethyl-1H-pyrazol-1-yl)-6-methylpyrimidine (HL1) and 2-(2-hydroxyphenyl)-
4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-methylpyrimidine (HL2), were synthesized by the condensation of
4-hydrazinyl-2-(2-hydroxyphenyl)-6-methylpyrimidine with acetylacetone and dibenzoylmethane. In solution,
HL1 and HL2 do not exhibit luminescence due to efficient non-radiative deactivation through S0/S1 conical
intersection of non-planar nature, whereas in the solid state they show dual emission associated with
phosphorescence at 500–700 nm and fluorescence at 400–500 nm. Phosphorescence is not related to ESIPT
and occurs in the enol form (E) in accordance with the Kasha rule, TE1 - SE0. In contrast, fluorescence follows
the proton transfer process and corresponds to the anti-Kasha SK2 - SK0 transition in the tautomeric keto form
Received 6th February 2023, (K), which is caused by an extraordinarily large S2–S1 energy gap (ca. 0.9 eV) and, consequently, low S2 - S1
Accepted 4th March 2023 internal conversion rate. The fluorescence/phosphorescence intensity ratio is temperature-dependent for
DOI: 10.1039/d3nj00570d HL1, resulting in the emission color change from yellow-green at 77 K to blue-green at 300 K, while HL2
glows in the orange region in the whole temperature range owing to the predominant contribution of
rsc.li/njc phosphorescence.
Introduction to-enol transformation, i.e. the ground state intramolecular

proton transfer (GSIPT).
Organic compounds featuring short O–H N intramolecular Electronic properties of ESIPT-capable molecules and therefore
hydrogen bonds between aromatic/heteroaromatic moieties of the ESIPT and GSIPT abilities of such molecules can be tuned
their molecules can show proton transfer reactions upon through introducing various substituents or heteroatoms,16–36
photoexcitation.1–15 These excited state intramolecular proton expanding the p-system,37–40 binding metal ions,41–54 protona-
transfer (ESIPT) reactions lead to fast excited state enol-to-keto tion/deprotonation,55–64 solvent effects,65–69 etc. The synthetic
tautomerization of ESIPT-capable molecules (Scheme 1). Radia- flexibility of such molecules is based on established synthetic
tive relaxation of the keto-form occurs normally with significant methods of organic chemistry and provides researchers with
Stokes shifts due to noticeable structural reorganization of the almost unlimited options for the rational design and modification
molecule which accompanies the ESIPT process. After convert-
ing to the ground state, the molecule undergoes a reverse keto-
a
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of
Sciences, 3, Acad. Lavrentiev Ave., Novosibirsk, 630090, Russia.
E-mail: shekhovtsov@niic.nsc.ru, bushuev@niic.nsc.ru; Fax: +7 383 330 94 89;
Tel: +7 383 316 51 43
b
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of
Russian Academy of Sciences, 9, Acad. Lavrentiev Ave., Novosibirsk, 630090,
Russia
† Electronic supplementary information (ESI) available: Spectral, structural and
computational data. CCDC 2238330 (HL1) and 2238332 (HL2). For ESI and
crystallographic data in CIF or other electronic format see DOI: https://doi.org/ Scheme 1 Keto-enol tautomerization processes in ESIPT-capable mole-
10.1039/d3nj00570d cules featuring short O–H N intramolecular hydrogen bonds.
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023 New J. Chem., 2023, 47, 6361–6377 | 6361
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of various ESIPT-capable scaffolds.70–74 The tuneability of the

properties of ESIPT-fluorophores coupled with their extreme
sensitivity to external and internal stimuli makes them an appeal-
ing platform for a plethora practical applications. For example,

these fluorophores are widely used in analytical chemistry, and
the design of ESIPT-capable sensors for analytes of different
Scheme 3 Structural formulae of HL (previously synthesized compound,
nature (cations, anions, molecules) has become one of the highly ref. 82), HL1 and HL2 (synthesized in the present work).
grown interdisciplinary areas in recent years.75–79 Due to spatial
separation of the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) ESIPT-fluoro- crossing in both compounds which leads to TADF. Due to the
phores can have narrow singlet–triplet energy gaps facilitating presence of local energy minima in the keto form in the S0 state,
thermally activated delayed fluorescence (TADF).80–83 Some ESIPT- both compounds were able to be excited not only in the enol form
capable organic compounds are known to exhibit phospho- but also in the tautomeric keto one.123
rescence84,85 and even room temperature phosphorescence In the context of multiple emission mechanisms observed in HL
(RTP).31,32,86,87 Both RTP and TADF involve singlet–triplet transi- and Zn(HL)Cl2 we endeavour to explore the impact of isomerism on
tions (intersystem crossing and reverse intersystem crossing) ESIPT and luminescence of (azolyl)(2-hydroxyphenyl)pyrimidines.
whose efficiency in purely organic materials can be improved With this goal in mind we turned to the synthesis of ESIPT-capable
through introducing heavy atoms and/or different orbital char- molecules with a new (pyrazolyl)(2-hydroxyphenyl)pyrimidine core,
acters of the singlet and triplet states according to El-Sayed’s namely the 2-(2-hydroxyphenyl)-4-(1H-pyrazol-1-yl)pyrimidine one.
rule.88 Compounds exhibiting efficient TADF and RTP can find The synthesis of pyrimidine-based compounds featuring this iso-
their applications in manufacturing organic light emitting diodes. meric core is of importance for gaining insights into how the
Isomerism of ESIPT-capable molecules provides researchers change in the position of the 2-hydroxyphenyl group in the pyrimi-
with a new powerful tool to gain insights into the interplay of dine ring affects deactivation channels associated with radiative
proton transfer processes and emission properties. However, and non-radiative processes. Here we report the synthesis, struc-
studies of isomeric ESIPT-capable molecules are relatively tures, ESIPT-capabilities and luminescence of 2-(2-hydroxyphenyl)-
scarce in the literature.89–103 4-(3,5-dimethyl-1H-pyrazol-1-yl)-6-methylpyrimidine (HL1) and 2-(2-
Due to the presence of two nitrogen atoms in the positions hydroxyphenyl)-4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-methylpyrimidine
1 and 3 of the six-membered cycle, the pyrimidine ring offers (HL2) (Scheme 3).
particularly interesting opportunities for the synthesis of iso-
meric molecules.104,105 For example, introducing the proton- Experimental section
donating 2-hydroxyphenyl group in the positions 2 or 4(6) of the
pyrimidine ring ensures the formation of a short O–H N General information
intramolecular hydrogen bond as a pre-requisite for ESIPT Elemental analysis was performed with a EuroEA3000 analyzer
and leads to two isomeric series of ESIPT-capable molecules using standard technique. The IR spectra were recorded in KBr
(Scheme 2). on a Bruker Vector-22 spectrometer.1H and 13C NMR spectra
Earlier our group synthesized 4-(3,5-dimethyl-1H-pyrazol-1- were recorded on Bruker AV-400 (400.13 and 100.61 MHz) and
yl)-6-(2-hydroxyphenyl)pyrimidine (HL) as the first example of Bruker DRX-500 (500.13 and 125.76 MHz) spectrometers using
ESIPT-capable (azolyl)(2-hydroxyphenyl)pyrimidines (Scheme 3).106 the residual signals of the solvent (CDCl3) at 7.24 ppm for 1H
Importantly, this compound exhibits dual emission and is capable and 76.9 ppm for 13C with respect to TMS as the internal
of binding metal ions. Both HL and its complex Zn(HL)Cl2 standard. Corrected photoluminescence spectra were recorded
appeared to feature luminescence in violation of Kasha’s rule, on a Fluorolog 3 spectrometer (Horiba Jobin Yvon).
which states that emission occurs in appreciable yield only from
the lowest excited state, e.g. S1 or T1. Although exceptions to this Synthesis of 2-(2-hydroxyphenyl)-4-(3,5-dimethyl-1H-pyrazol-1-
rule are known,107–117 they are quite rare, and most of them are yl)-6-methylpyrimidine (HL1)
related to azulene derivatives.118–122 Surprisingly, HL and Zn(HL)Cl2 A mixture of 4-hydrazinyl-2-(2-hydroxyphenyl)-6-methylpyri-
exhibit a unique interplay of anti-Kasha fluorescence (S2 - S0) and midine (1.08 g, 5 mmol) and acetylacetone (0.6 ml, 6 mmol)
anti-Kasha phosphorescence (T2 - S0), which is caused by extra- in EtOH (25 ml) was boiled for 5 h. After cooling down to room
ordinarily large S2–S1 and T2–T1 energy gaps.123 Furthermore, temperature, the residue formed was filtered off, washed with
narrow S2–T2 energy gaps and different orbital characters of these EtOH and purified by column chromatography (SiO2, CHCl3) to
states (1pp* and 3np*, respectively) facilitate reverse intersystem give the title compound. Yield: 1.3 g (93%), m.p. 171–172 1C.
Anal. calc. for C16H16N4O: C, 68.55; H, 5.75; N, 19.99. Found: C,
68.19; H, 5.72; N, 19.97%. 1H NMR (CDCl3, 300.13 MHz) d
(ppm): 13.67 (br. s, 1H, OH), 8.31 (dd, 1H, J = 8.2, 1.7 Hz, 6 0 -
HPh), 7.67 (d, 1H, J = 0.5 Hz, 5-Hpyrimidine), 7.37 (ddd, 1H, J = 8.2,
7.1, 1.7 Hz, 4 0 -HPh), 7.01 (dd, 1H, J = 8.2, 1.1 Hz, 3 0 -HPh), 6.92
Scheme 2 Isomeric ESIPT-capable (2-hydroxyphenyl)pyrimidines. (ddd, 1H, J = 8.2, 7.1, 1.1 Hz, 5 0 -HPh), 6.06 (s, 1H, 400 -Hpyrazole),
6362 | New J. Chem., 2023, 47, 6361–6377 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023
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2.85 (d, 3H, J = 0.6 Hz, Me), 2.58 (d, 3H, J = 0.6 Hz, Me), 2.29 (s, (25%), B3LYP provides absorption and emission energies that
3H, Me). 13C NMR (CDCl3, 100.61 MHz) d (ppm): 165.66, 164.13, are closer to the experimental data, while PBE0 tends to blue-
160.79, 159.29, 151.89, 143.02, 133.01, 128.82, 118.72, 118.59, shift some vertical transitions for both HL1 and HL2 (ESI,†
117.86, 111.04, 106.64, 23.70, 15.97, 13.63. IR (KBr pellet, n/cm1): Fig. S16 and S17). Functionals with a higher percentage of HF
1601s, 1581vs, 1552m, 1487m, 1468m, 1439s, 1375s, 1306m, exchange, such as BMK (42%) or M062X (54%), would follow
1254m, 1221w, 1146w, 1032w, 970w, 849m, 804w, 758m, 739w. the same trend and provide even more blue-shifted vertical
transitions. Therefore, our choice of the B3LYP functional is
Synthesis of 2-(2-hydroxyphenyl)-4-(3,5-diphenyl-1H-pyrazol-1-yl)- justified by the good correlation between the experimental and
6-methylpyrimidine (HL2) calculated data. The 6-31+G(d) basis set was used for all atoms.
A mixture of 4-hydrazinyl-2-(2-hydroxyphenyl)-6-methylpyrimidine Absorption spectra were calculated on ground state geometries
(0.49 g, 2.4 mmol) and dibenzoylmethane (0.62 g, 2.8 mmol) in using TDDFT. Singlet excited state geometries (S1) as well as
AcOH (14 ml) was boiled for 30 h. After cooling down to room S1 - S0 and S2 - S0 fluorescence energies were also deter-
temperature, the residue formed was filtered off, washed with mined using the TDDFT approach. The optimizations of the
AcOH, EtOH and purified by column chromatography (SiO2, lowest triplet excited state (T1) geometries of HL1 and HL2 were
CH2Cl2). Yield: 0.41 g (42%), m. p. 166–167 1C. Anal. calc. for carried out by an unrestricted DFT (uDFT) method. Subsequent
C26H20N4O: C, 77.21; H, 4.98; N, 13.85. Found: C, 77.24; H, 4.81; N, single-point TDDFT computations on T1 optimized geometries
13.59%. 1H NMR (CDCl3, 400.13 MHz) d: 13.27 (br. s, 1H, OH), revealed T1 - S0 phosphorescence energies. Relaxed T1 state
7.96–7.94 (m, 2H, 300 -HPh), 7.83 (s, 1H, 5-Hpyrimidine), 7.49–7.39 (m, geometries can also be obtained using TDDFT approach, however,
8H, 300 -HPh and 500 -HPh), 7.24 (m, 1H, 4 0 -HPh), 6.88 (dd, 1H, J = 8.2, the uDFT method is more preferable because it requires much
1.0 Hz, 30 -HPh), 6.82 (s, 1H, 400 -Hpyrazole), 6.77 (m, 1H, 6 0 -H), 6.53 less computational cost. In the case of simulating absorption
(m, 1H, 5 0 -HPh), 2.63 (s, 3H, Me). 13C NMR (CDCl3, 125.75 MHz) d spectra in acetonitrile, the solvent effects of acetonitrile molecules
(ppm): 162.28, 163.76, 160.54, 158.52, 153.67, 146.44, 132.87, were considered by the polarizable continuum model (PCM).
132.67, 131.94, 129.49, 128.86, 128.84, 128.69, 128.24, 127.99, All other computations were performed in the gas phase. The
126.03, 118.23, 118.16, 117.34, 109.34, 107.28, 23.89. IR (KBr D3 version of Grimme’s dispersion with Becke–Johnson damping
pellet, n/cm1): 1597s, 1572vs, 1552s, 1489m, 1464s, 1448s, was employed for each calculation. Potential energy curves (PECs)
1375vs, 1302m, 1252m, 1228m, 1205m, 1180m, 1151m, 1115w, of the desired states (S0, S1, S2, T1) along the proton transfer
1105w, 1076w, 1061w, 1026w, 1001w, 985w, 951m, 912w, 852m, reaction were plotted by scanning the O H bond distance
800m, 768s, 758s, 710w, 696m, 646w, 608w. between 0.95 and 2.0 Å with a step of 0.05 Å. All frequencies in
the harmonic approximation for the calculated global minimum
X-ray crystal structures energy geometries are positive, confirming that the optimized
Single-crystal XRD data for the compounds HL1 and HL2 (ESI,† molecular geometries correspond to the real minima on the
Tables S1–S3) were collected at 150 K with a Bruker D8 Venture potential energy surfaces. The atomic coordinates of all optimized
diffractometer with a CMOS PHOTON III detector and ImS 3.0 geometries are given in ESI,† Tables S4–S16. The geometries
microfocus source (MoKa radiation (l = 0.71073 Å), collimating and molecular orbitals were visualized using ChemCraft
Montel mirrors). The crystal structures were solved using the software.133
ShelXT124 and were refined using ShelXL125 programs with
Olex2 GUI.126 Atomic displacement parameters for non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were placed Results and discussion
geometrically. The structures of HL1 and HL2 were deposited to the
Cambridge Crystallographic Data Centre (CCDC) as a supplemen- Synthesis and crystal structures of HL1 and HL2
tary publication, CCDC 2238330 and 2238332.† The target compounds HL1 and HL2 were synthesized by the
condensation of 4-hydrazinyl-2-(2-hydroxyphenyl)-6-methylpyri-
Computational details midine with acetylacetone and dibenzoylmethane, respectively
Quantum chemical calculations were carried out using density (Scheme 4). Whereas the synthesis of HL1 can be performed in
functional theory (DFT) and time-dependent DFT (TDDFT) EtOH under reflux within 5 h., the synthesis of HL2 requires
methods in Gaussian 16 software package.127 When it comes higher temperature and much more time.
to describing states with charge transfer nature, it is important HL1 crystallizes in the monoclinic crystal system in the space
to choose the right functional. We used the hybrid exchange- group P21/n. The HL1 molecule is practically planar (Fig. 1). The
correlation functional B3LYP128–131 with 20% fraction of Har- 4-(1H-pyrazol-1-yl)pyrimidine moiety in the HL1 molecule
tree–Fock exchange because most previous theoretical studies, adopts the transoid conformation with the N2pyrazole–N1pyrazole–
including our recent ones describing the emission mechanisms C4pyrimidine–N3pyrimidine torsion of 1771 due to the repulsion of
of pyrimidine- and benzimidazole-based ESIPT-dyes, have N2pyrazole and N3pyrimidine lone pairs. As a result, the methyl group
demonstrated its good performance in modeling the photo- in the position 5 of the pyrazole cycle prevents the formation
physical and photochemical properties of proton transfer of hydrogen bonds with the N3pyrimidine atom and the short
systems.123,132 Compared to another popular hybrid functional intramolecular O–H N hydrogen bond is formed with the
PBE0 with slightly higher fraction of Hartree–Fock exchange N1pyrimidine atom instead (O N 2.59 Å).
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due to the steric bulk this phenyl group is rotated by ca. 551
relative to the pyrazole cycle. The torsion between the second
phenyl group and the pyrazole cycle is significantly smaller
and does not exceed 101. On the other hand, the 2-(2-hydroxy-
phenyl)pyrimidine moiety is practically planar and is stabilized
by a short intramolecular hydrogen bond between the OH group
and the N1pyrimidine atom (O N 2.58 Å).
The phenyl groups, which make the 4-(3,5-diphenyl-1H-
pyrazol-1-yl)pyrimidine moiety in the structure of HL2 non-
planar, significantly affect the packing of molecules. In contrast
to the structure of HL1, there are no p-stacking interactions in
Scheme 4 Synthesis of HL1 and HL2.
the crystal structure of HL2. Instead, the C–H N weak hydrogen
bonds and the C–H C van der Waals interactions assemble the
HL2 molecules into 2D supramolecular layers. The layers are
connected to each other by weak van der Waals interactions only
(ESI,† Fig. S10–S12).
Absorption properties and mechanisms

In acetonitrile, both HL1 and HL2 absorb light in the ultraviolet
region up to ca. 380 nm (Fig. 3 and 4). The absorption spectra of
these compounds are dominated by two bands. The low-energy
band is centred at 318 and 321 nm for HL1 and HL2, respec-
tively, while the high-energy band is centred at 265 and 258 nm.
Noteworthy, the relative intensities of these two absorption
bands differ notably for two compounds. The diffuse reflec-
Fig. 1 Molecular structure of HL1. tance spectra, which stand as analogues of absorption in the
solid state, mostly lie in the same UV region as the absorption
spectra, however, they also span a little to the visible region (up
Practically planar HL1 molecules are assembled by p- to 400 nm for HL1 and up to 430 nm for HL2, Fig. 3 and 4).
stacking and van der Waals interactions into 1D supramolecu- Theoretical absorption spectra were calculated and com-
lar chains running along the crystallographic b axis. The chains pared with the experimental data in order to elucidate the
form the supramolecular 3D structure of this compound by absorption mechanisms (Fig. 3 and 4). Since HL1 and HL2 can
means of C–H C and C–H H–C van der Waals interactions exist in two tautomeric forms, for the sake of simplicity here
(ESI,† Fig. S7–S9). and further we will use the abbreviations E-HL for the enol
HL2 crystallizes in the triclinic crystal system in the space form of the molecule and K-HL for the keto form (Scheme 5).
group P1% . Although the 4-(1H-pyrazol-1-yl)pyrimidine moiety
adopts the transoid conformation (Fig. 2), the N2pyrazole–N1pyrazole–
C4pyrimidine–N3pyrimidine torsion is smaller than this one in the
structure of HL1 (1611 vs. 1771) due to significant steric bulk of
the phenyl group in the position 5 of the pyrazole ring. Moreover,
Fig. 3 Absorption and diffuse reflectance spectra of HL1 MeCN. Vertical

bars display the positions and oscillator strengths of the computed singlet-
Fig. 2 Molecular structure of HL2. to-singlet electronic transitions.
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Fig. 4 Absorption and diffuse reflectance spectra of HL2 in MeCN.

Fig. 5 The potential energy curves (PECs) of the S0, S1, S2 and T1 states of
Vertical bars display the positions and oscillator strengths of the computed
HL1 along the proton transfer path O–H N. The arrows show the energy
singlet-to-singlet electronic transitions.
minima.
The superscripts E or K will also be used with regard to the

energy minima of a particular state, e.g. SK1 is the energy
minimum of the S1 state in the K-HL form.
Potential energy curves (PECs) of excited and ground states
of HL1 and HL2 are shown in Fig. 5 and 6. Since absorption
occurs from the energy minima of the ground state, it is first
necessary to examine the PECs of the S0 state for HL1 and HL2
along the proton transfer reaction (Fig. 5 and ESI,† Fig. S13).
These curves reveal that there is only one global energy mini-
mum in the E-HL form for both compounds. The corres-
ponding SE0 geometries are in good agreement with the X-ray
single crystal structures. Vertical singlet-to-singlet transitions
SE0 - SEn were computed at these geometries. The positions and
relative oscillator strengths of two brightest transitions are in
excellent accordance with the positions and relative intensities
of two experimental absorption bands (Fig. 3 and 4), showing
the relevance of the functional and basis set used through this
study. The first singlet-to-singlet absorption, SE0 - SE1, is
calculated at 321 and 334 nm for E-HL1 and E-HL2, respectively. Fig. 6 The PECs of the S1 and S2 states of HL1 along the dihedral angle y
between the planes of hydroxyphenyl and pyrimidine moieties. The arrows
In terms of molecular orbitals, it corresponds to HOMO - show the energy minima. The geometry close to the S0/S1 conical inter-
LUMO transition with charge transfer nature (Fig. 3 and 4). section (CI) is also shown.
HOMO is a p-orbital located on the proton-donating hydroxy-
phenyl moiety, while LUMO a p*-orbital that is mostly located
on the proton-accepting pyrimidine moiety. In the case of
E-HL2, LUMO is also partially contributed by the phenyl sub-
stituents to the pyrazole moiety, resulting in a slight red-shift of
SE0 - SE1 transition as compared to E-HL1 due to an increase in
the distance of charge transfer.
The SE0 - SE1 absorption is brightest ( f = 0.2195) for E-HL1 in
the low-energy region (labs 4 300 nm) and is therefore fully
responsible for the appearance of the low-energy band in the
absorption spectrum. However, this is not the case for E-HL2
because its second singlet-to-singlet transition, SE0 - SE2 (lcalc =
324 nm, f = 0.4781), is much more intense than the first one ( f =
0.0622, Fig. 4). It is formed by HOMO1 - LUMO transition
Scheme 5 Tautomeric forms of HL1 (R = Me) and HL2 (R = Ph). involving charge transfer from the 3,5-diphenyl-1H-pyrazol-1-yl
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group to pyrimidine. A number of vertical transitions with a both compounds. The high-energy absorption band appears due
relatively low oscillator strength ( f o 0.1) in the region 240– to SE0 - SE13 (lcalc = 255 nm, f = 0.2222) and SE0 - SE7 (lcalc =
325 nm do not contribute essentially to the absorption spectra of 268 nm, f = 0.7302) transitions for E-HL1 and E-HL2, respectively.
Fig. 7 Excitation and emission spectra of HL1 and HL2 in the solid state at 77 K (a) and (b), at 300 K (e) and (f). Temperature dependence of the excitation
and emission spectra (c) and (d).
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The former one is HOMO2 - LUMO transition with locally (Fig. 7(c) and (d)). The relative contributions of two emission
excited character, i.e. without significant charge transfer, while the bands remain essentially the same for HL2, so the emission
latter one is HOMO - LUMO+2 transition implying charge color of HL2 does not change significantly with temperature.
transfer from the hydroxyphenyl part to the 3,5-diphenylpyrazole On the contrary, the relative contribution of the high-energy
part (Fig. 4). To summarize, despite the fact that the first singlet- band increases markedly for HL1 when going from 77 K to
to-singlet absorption has the same mechanism for both com- 300 K, causing the emission color to change from yellow-green
pounds, the mechanisms of the most intense transitions differ at 77 K to blue-green at 300 K. Noteworthy, the positions of the
significantly, mainly due to the presence of the phenyl substitu- maxima of high- and low-energy bands change negligibly upon
ents in the case of E-HL2, which may serve both as efficient heating.
reservoirs for donating or accepting electron density. At 300 K, the emission spectrum of HL1 depends on excita-
tion wavelength: the high-energy emission band is prevalent at
Photoluminescence properties lex = 280–340 and 400–420 nm, whereas the low-energy emis-
In the solid state, HL1 and HL2 exhibit photoluminescence in sion band becomes dominant at lex = 360–380 nm (Fig. 7(e)).
the visible region (Fig. 7). The emission properties were studied In contrast, the low-energy band is always dominant for HL2 at
in the temperature range 77–300 K. At 77 K, two bands are 300 K regardless of the excitation energy (Fig. 7(f)). The excita-
observed in the luminescence spectra (Fig. 7(a) and (b)). The tion spectra at 300 K are similar to those at 77 K.
low-energy band is localized in the region 500–700 nm with a The luminescence decay curves for HL1 and HL2 are multi-
maximum at 536 and 577 nm for HL1 and HL2, respectively, exponential (ESI,† Fig. S14 and S15). Both short lifetimes of
whereas the high-energy band is located at 425–500 nm for HL1 excited states in the nanosecond range (t = 5 ns for HL1; t1 =
(lmax = 472 nm) and at 400–500 nm for HL2 (lmax = 414 and 3 ns, t2 = 17 ns for HL2) and long lifetimes in the microsecond
439 nm). The low-energy band is an order of magnitude more range (t = 178 ms for HL1; t = 28 ms for HL2) were observed,
intense than the high-energy band for HL2 and only twice more indicating an interplay of fluorescence and phosphorescence in
intense than the high-energy band for HL1. Such difference in the compounds under study. Time-resolved emission spectrum
relative intensities brings a noticeable change in the emission of HL1 with a time delay of 100 ms was recorded and compared
color at 77 K: HL1 luminesces in the yellow-green region due to with the steady state spectrum in order to find out which band
an almost equal contribution of two aforementioned bands; is associated with which radiative mechanism (Fig. 8). The
HL2 glows in the orange region owing to the predominant time-resolved spectrum shows a single band in the region
contribution of the low-energy band (Fig. 8). Varying the 480–700 nm centred at ca. 560 nm. Therefore, the low-energy
excitation energy from lex = 280 nm to lex = 400 nm leads to emission band, which is located in the same region, is attrib-
very small changes (o5 nm) in the position of the photolumi- uted to phosphorescence. Consequently, the high-energy emis-
nescence band maxima. The excitation spectra recorded at the sion band is attributed to fluorescence. The fluorescence
emission band maxima are similar; both bands can be effec- relaxation pathway is fully drained when recording spectrum
tively excited in the entire UV region (lex o 380 nm). with the 100 ms time delay, so the high-energy band is not
Upon heating from 77 K to 300 K, the emission intensity observed in the time-resolved spectrum.
decreases due to an increase in the contribution of non- The photoluminescence quantum yield is 2% for HL1 and
radiative decay processes stimulated by various vibrations, o1% for HL2 at 300 K. Compared to the solid state, HL1 and
some of which are partially frozen at low temperatures HL2 are non-emissive in solution. Weak emission in the solid
Fig. 8 CIE 1931 diagram showing the chromaticity of emission of HL1 and HL2 in the solid state at different temperatures (left); time-resolved emission
spectrum of HL1 with a time delay of 0.1 ms (right).
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state and its absence in solution indicate the presence of substituents to the phosphorescence mechanism of HL2
efficient non-radiative decay channels for both ESIPT- (Fig. 9).
emitters. In the next section, we pinpoint possible radiative Apart from the TE1 minimum, another minimum, TK1 (O–H
and non-radiative deactivation pathways by quantum chemical 1.836 Å, O–H N 2.663 Å), appears on the PEC of the T1 state in
computations. the K-HL1 form (Fig. 5). The energy barrier for the TE1 - TK1
ESIPT process is ca. 3 kJ mol1. The TK1 minimum is thermo-
dynamically more stable than TE1 by 47 kJ mol1. However, the
The mechanisms of fluorescence and phosphorescence: computed TK1 - SK0 phosphorescence wavelength is in the
a theoretical investigation infrared region (834 nm) and is hugely overestimated compared
From a theoretical perspective, emission is a transition from to the position of the experimental phosphorescence band.
the energy minimum of a certain excited state to the ground Owing to the fact that we do not observe luminescence in the
state. Thus, to study the emission mechanisms we need to infrared region, we presume that the molecules do not exhibit
optimize the geometries of the excited states. Phosphorescence the TK1 - SK0 radiative transition for the following reasons:
is a spin-forbidden transition that occurs from a triplet excited (i) the molecules of HL1 may not populate the TK1 minimum
state. The PEC of the T1 state of HL1 reveals two minima, TE1 and since the TE1 - TK1 energy barrier effectively impedes the ESIPT
TK1 (Fig. 5). In the E-HL1 form, the triplet manifold can be process, leading to trapping of excited molecules only in the
populated after SE0 - SE1 absorption followed by SE1 - TE1 TE1 minimum; (ii) even if some molecules populate the TK1
intersystem crossing. Compared to SE0, the geometry of the TE1 minimum, they decay non-radiatively through various chan-
minimum is characterized by a slightly elongated O–H distance nels, e.g. via S0/T1 conical intersections. The same is true for
(1.023 Å for TE1 vs. 1.004 Å for SE0, Table 1) and a shortened HL2 as its TK1 - SK0 transition is also calculated in the infrared
O–H N hydrogen bond (2.565 Å for TE1 vs. 2.592 Å for SE0), region at 965 nm and therefore it certainly cannot be related to
indicating strengthening of the hydrogen bond in the T1 state. any experimental emission band.
The calculated TE1 - SE0 phosphorescence wavelength (525 nm) In contrast to the T1 state, the ESIPT process is barrierless in
is in excellent agreement with the maximum of the low-energy the S1 state (Fig. 5). According to the PECs, after SE0 - SE1
emission band of HL1 (536 nm). According to the analysis of excitation and subsequent SE1 - SK1 proton transfer, the mole-
frontier molecular orbitals, TE1 - SE0 is a LUMO - HOMO cules of HL1 populate the SK1 minimum (O–H 1.797 Å, O–H N
transition, with LUMO (p*) located on the hydroxyphenyl and 2.675 Å). The fluorescence of HL1 from the first singlet excited
pyrimidine moieties and HOMO (p) located only on the hydro- state, SK1 - SK0, is computed at 979 nm, while the experimental
xyphenyl moiety (Fig. 9). Thus, we attribute the low-energy fluorescence band is centred at 472 nm. A huge difference
phosphorescence band of HL1 to the TE1 - SE0 transition of between these two values indicates that we cannot relate the
the E-HL1 form (Fig. 10), which involves partial charge transfer fluorescence of HL1 to the SK1 - SK0 transition.
from the proton-accepting pyrimidine part to the proton- In order to understand why emission from the SK1 minimum
donating hydroxyphenyl part (this is directly opposite to the is not observed, we attempted to investigate a possible mecha-
SE0 - SE1 absorption mechanism described above). In the case of nism for its non-radiative decay. According to previous research
HL2, the computed TE1 - SE0 wavelength (525 nm) is same as on ESIPT-capable compounds, the proton transfer process can
that for HL1, which is justified by the similar electron density lead to a radiationless deactivation via a conical intersection
distribution on HOMO and LUMO for these two compounds as (CI) of non-planar nature (in other words, through a so-called
well as by the absence of the contribution of the phenyl twisted intramolecular charge transfer (TICT) state).134–144 We
noticed that the geometries of the S1 state with an O–H distance
constraint greater than 1.8 Å cannot be optimized due to
Table 1 The most relevant geometric parameters for the optimized oscillations around a CPh–CPym bond connecting the hydroxy-
geometries of HL1 and HL2 phenyl and pyrimidine moieties. Unconstrained geometry opti-
mization of the S1 state with l(O–H) 4 1.8 Å directly leads to a
Cmpd. State O–H, Å O–H N, Å y1,a
non-planar geometry (near-CI geometry in Fig. 6), which arises
HL1 SE0 1.004 2.592 0.02 due to the twist by 831 around the CPh–CPym bond. One of the
SK1 1.797 2.675 0.17 factors which facilitates this torsion is the small overlap
SK2 1.692 2.596 7.43
between HOMO and LUMO at the SK1 geometry, which in turn
TE1 1.023 2.565 0.00
TK1 1.836 2.663 0.01 reduces p-conjugation between the hydroxyphenyl and pyrimi-
near-CIb 3.163 3.305 83.05 dine moieties and even allows breaking of the hydrogen bond
HL2 SE0 1.002 2.606 2.43 during the twist. The energy gap between the S0 and S1 states at
SK1 1.791 2.671 2.25
the near-CI geometry is only 0.7 kJ mol1. Although the precise
SK2 1.707 2.606 0.67
TE1 1.022 2.575 0.37 geometry of the conical intersection cannot be optimized using
TK1 1.875 2.686 1.84 TDDFT, such low energy gap may serve as an indirect evidence
a of its existence. The near-CI geometry is more stable than SK1 by
y is the dihedral angle between the planes of hydroxyphenyl and
pyrimidine moieties. b Geometry that is close to the conical intersec- 19.4 kJ mol1. The dihedral angle y scan shows that the energy
tion between the S0 and S1 states. barrier when going from SK1 with y = 01 to near-CI geometry with
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Fig. 9 Frontier molecular orbitals related to the photophysical processes in HL1 and HL2.
y = 831 is so negligible (o0.1 kJ mol1) that it can be easily accordance with the maximum of the high-energy emission band of
overcome to reach the conical intersection. Thus, owing to (i) HL1 (472 nm). It corresponds to LUMO+1 - HOMO transition
an experimental observation that HL1 does not emit in solution (Fig. 9). As for the S1 state, we also performed the dihedral angle y
and weakly emits in the solid state and (ii) a theoretical scan for the S2 state in order to test its stability towards twisting.
observation that the near-CI geometry in the S1 state is prefer- Upon the increase in the dihedral angle, the energy barrier reaches
able both thermodynamically and kinetically, we believe that ca. 3 kJ mol1, indicating that the SK2 form is much more stable than
the non-radiative deactivation via S0/S1 conical intersection is SK1 (Fig. 6). In other words, twisting is unfavorable in the S2 state,
responsible for emission quenching of HL1. which can be explained by the following observations: (i) LUMO+1
In search of other possible fluorescence pathways, we examined overlaps well with HOMO, providing efficient p-conjugation
the PEC of the higher-lying S2 state and found the SK2 minimum between the aromatic moieties; (ii) the O–H N hydrogen bond is
there (O–H 1.692 Å, O–H N 2.596 Å, Fig. 5 and Table 1). The stronger in the S2 state as compared to S1 (2.596 Å for SK2 vs. 2.675 Å
calculated SK2 - SK0 fluorescence wavelength (505 nm) is in good for SK1), thus more energy is required to break it.
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Paper NJC
All compounds exhibit SK2 - SK0 fluorescence associated with the

ESIPT process from the proton-donating oxygen atom to the
proton-accepting nitrogen atom. The fluorescence maxima of HL3
and HL (at ca. 550 nm) are red-shifted by ca. 100 nm as compared
to HL1 and HL2. In large contrast to HL1 and HL2, the fluorescence
of both HL3 and HL is predominantly excited in the visible region
at lex E 450 nm. For this reason HL3 and HL demonstrate
extremely small Stokes shifts of ca. 100 nm. At the same time,
HL1 and HL2 are most effectively excited in the UV region (lex o
380 nm). The reason underlying the difference in the excitation
spectra between HL1/HL2 and HL3/HL is related to the number of
minima on the PEC of the S0 state. In addition to the global energy
minimum SE0, the second minimum, SK0, appears on the PECs of
HL3 and HL. Singlet-to-singlet excitations from SK0 are red-shifted
compared to those from SE0, resulting in the red-shift of the
excitation spectrum from the UV region to the visible region. The
excitations from SK0 are not possible for HL1 and HL2 since there is
only one minimum on the PEC of the ground state, SE0. In addition,
the S2–T2 energy gap is negligibly small in the case of HL (o0.1 eV),
which facilitates efficient T2 - S2 - S0 TADF and increases the
photoluminescence efficiency up to 7%, whereas in HL1 and HL2
Fig. 10 Photophysical and photochemical properties of HL1 and HL2 in TADF is not favorable due to large S2–T2 energy gaps. Thus,
the solid state summarized in a simplified energy level diagram. IC – although HL and HL1 are structurally similar compounds, they
internal conversion; ISC – intersystem crossing. exhibit drastically different photophysical properties.
Therefore, we assume that HL1 violates Kasha’s rule and

emits from the S2 state (Fig. 10), which is a rare phenomenon Conclusions
for purely organic emitters. In addition to the arguments
presented above, the following points also support this conclu- In this work, new pyrimidine-based compounds, 2-(2-hydroxy-
sion. (i) Classically, the energy gaps between the singlet excited phenyl)-4-(3,5-dimethyl-1H-pyrazol-1-yl)-6-methylpyrimidine (HL1)
states in conventional organic dyes are as low as 0.1–0.3 eV, and 2-(2-hydroxyphenyl)-4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-methylpyri-
meaning that even after excitation to a certain higher-lying midine (HL2), were synthesized and studied. These compounds
singlet excited state, the molecules would rapidly decay to S1. feature short O–H N intramolecular hydrogen bonds (O N
However, this is not the case for HL1 as the energy gap between E 2.6 Å) as a prerequisite for excited state intramolecular
the S1 and S2 states is 0.86 eV (or 83 kJ mol1, Fig. 5). According proton transfer (ESIPT) and exhibit photoluminescence in the
to the energy gap law, such large gap slows down the rate of solid state. The emission spectra of both compounds are
SK2 - SK1 internal conversion, allowing a certain amount of dominated by two bands. The low-energy band at 500–
excited molecules to emit directly from the SK2 minimum. (ii) 700 nm with excited state lifetimes in the microsecond range
The oscillator strength for the SK2 - SK0 transition (0.1593) is an is related to phosphorescence, while the high-energy band at
order on magnitude higher than for the SK1 - SK0 transition 400–500 nm with nanosecond lifetimes is attributed to fluores-
(0.0102), so, from this perspective, S2 can be considered as a cence. HL1 luminesces in yellow-green region owing to approxi-
bright state and S1 – as a dark state. mately equal contribution of these two bands, whereas HL2
Similarly to HL1, the calculated wavelength of the SK1 - SK0 emits in orange region due to the predominant contribution of
transition for HL2 is in the infrared region (1024 nm), while the the low-energy band. According to quantum chemical compu-
wavelength of the SK2 - SK0 transition (506 nm) is in better tations, phosphorescence of HL1 and HL2 is not related to the
agreement with the experimental data. The oscillator strength ESIPT process and takes place in the enol form of the molecule,
for the former transition (0.0166) is ten times smaller than for TE1 - SE0. In contrast, fluorescence of both ESIPT-emitters
the latter one (0.1621); the S2–S1 energy gap is 0.95 eV. These occurs in the keto form (i.e. after proton transfer from the
facts point to the same emission mechanism for HL2 as for HL1, oxygen atom to the nitrogen atom) and corresponds to SK2 - SK0
i.e. to anti-Kasha SK2 - SK0 fluorescence. transition in violation of Kasha’s rule, which is a rather rare
Although anti-Kasha fluorescence behavior is rather rare, phenomenon for purely organic compounds. Importantly, the
we also observed it recently for ESIPT-capable compounds previously reported HL compound,106,123 which bears the same
1-hydroxy-5-methyl-2,4-di(pyridin-2-yl)-1H-imidazole (HL3)145 and organic scaffold as HL1 and differs in the position of the
4-(2-hydroxyphenyl)-6-(3,5-dimethyl-1H-pyrazol-1-yl)pyrimidine (HL, 2-hydroxyphenyl substituent only, also exhibits anomalous
isomeric to HL1, Scheme 3).123 Herein we want to present a brief anti-Kasha emission. Analysis of frontier molecular orbitals
comparison between the emission properties of HL1/HL2 and HL3/HL. reveals that TE1 - SE0 and SK2 - SK0 transitions involve charge
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and applications in fluorescent molecular probes and
theoretical results were funded by the Russian Science Founda-
luminescent materials, Phys. Chem. Chem. Phys., 2012,
tion (grant no. 21-13-00216, https://rscf.ru/en/project/21-13-
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Dual emission of ESIPT-capable

ESIPT-capable pyrimidine-based compounds featuring short O–H N intramolecular hydrogen bonds,

Introduction to-enol transformation, i.e. the ground state intramolecular

of various ESIPT-capable scaffolds.70–74 The tuneability of the

ing platform for a plethora practical applications. For example,

Absorption properties and mechanisms

Fig. 3 Absorption and diﬀuse reflectance spectra of HL1 MeCN. Vertical

Fig. 4 Absorption and diﬀuse reflectance spectra of HL2 in MeCN.

The superscripts E or K will also be used with regard to the

All compounds exhibit SK2 - SK0 fluorescence associated with the

Therefore, we assume that HL1 violates Kasha’s rule and

40 N. A. Shekhovtsov, E. B. Nikolaenkova, A. S. Berezin, 50 E. Papazoi, A. Douvali, S. A. Diamantis, G. S. Papaefstathiou,

61 A. S. Berezin, B. Selivanov, A. Danilenko, A. Sukhikh and ESIPT-Capable 4-(2-Hydroxyphenyl)-2-(Pyridin-2-yl)-1H-

pyrazol-1-yl)-6-methyl-2-(pyridin-2-yl)pyrimidines (R = H, Transfer to Structure Twisting and Aggregation, J. Phys. Chem.

H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., N. Vassilev, F. S. Kamounah, M. Pittelkow, A. Crochet,

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