Article
Cite This: Cryst. Growth Des. 2018, 18, 2795−2803
Designed Synthesis and Crystallization of Isomorphic Molecular
Gyroscopes with Cell-like Bilayer Self-Assemblies
Ma. Eugenia Ochoa,† Pablo Labra-Vázquez,‡ Norberto Farfán,‡ and Rosa Santillan*,†
†
Departamento de Química, Centro de Investigación y de Estudios Avanzados del IPN, 07360 CDMX, México
‡
Facultad de Química, Departamento de Química Orgánica, Universidad Nacional Autónoma de México, 04510 CDMX, México
*
S Supporting Information
ABSTRACT: Two molecular rotors featuring pyridine and
fluorobenzene rings as polar rotators and 9-octylfluorenyl
stators were synthesized. Their crystal structures were
established through SXRD techniques, crystallizing in the
monoclinic chiral P21 space group. The supramolecular
assemblies of both isomorphs showed an orientation of static
dipoles through the crystal lattice and the formation of
intriguing 2D layers that resemble cell membranes, a typical
example of an amphidynamic system. Small activation energies
and the modulation of the first-order hyperpolarizabilities of
these compounds as a function of rotational dynamics were
revealed through DFT computations at the CAM-B3LYP/M06-2X/cc-pVDZ level of theory and correlated with a potential use
of these materials as photonic switches.
1. INTRODUCTION
Amphidynamic systems, defined as 3D molecular arrays that,
despite their long-range phase order, also display fast molecular
dynamics, have the potential to act as molecular rotors, i.e.,
crystalline molecular machines that, when properly engineered,
may display efficient rotational work such as that of
macroscopic gyroscopes or compasses.1 These crystal systems,
expected to display interesting properties like dichroism and
birefringence,2 usually incorporate a 1,4-diethynylphenylene
ring linked at both ends to rigid frameworks that provide the
supramolecular information that dictates the crystal packing.
Our group of work has put intense collaborative efforts in
studying the rotational dynamics of molecular rotors possessing
diverse rigid steroidal frameworks linked through acetylenic
axles to 1,4-phenylene rotators.3−5 During the course of these
investigations, the possibility of controlling the rotational
dynamics of these molecular compasses like systems using a
magnetic stimulus became appealing.
Herein, we describe the synthesis and supramolecular
structure of molecular rotors featuring 9,9-dioctylfluorene
groups as stators and pyridine and fluorobenzene rings as
polar rotators. The static dipolar moments present in these
molecules are intended to facilitate control of rotational
dynamics upon application of an external magnetic field.
Through SXRD analysis of these systems, we found that they
present peculiar solid-state self-assemblies that resemble closely
cell membranes, as well as other supramolecular features that
make these crystalline isomorphs interesting systems to be
studied as molecular gyroscopes.
© 2018 American Chemical Society
pubs.acs.org/crystal
2. EXPERIMENTAL SECTION
2.1. General Experimental Considerations. Materials. All
starting materials were purchased from Sigma-Aldrich and used
without further purification. Solvents were purified by distillation over
appropriate drying agents. Compounds 2−4 were obtained following
reported methodologies;6−8 spectroscopic data are in good agreement.
Instrumentation. NMR spectra were recorded on Jeol ECA 500
and Jeol 270 MHz spectrometers using deuterated solvents; chemical
shifts for 1H and 13C NMR data are relative to the residual
nondeuterated solvent signal, fixed at δ = 7.26 ppm for 1H NMR
and δ = 77.00 ppm for 13C NMR. Infrared spectra were registered on
an FT-IR Varian ATR spectrometer. HRMS data were acquired using
an Agilent G1969A MS TOF spectrometer. Elemental analysis for
MR2 was determined on a Thermofinnigan Flash 1112 equipment
(CHONS). Absorption spectra were obtained in chloroform solutions
using a PerkinElmer Lambda 2S UV/vis spectrophotometer.
2.2. Synthetic Procedures. Synthesis of Molecular Rotors. 2,5-
Bis((9,9-dioctyl-fluoren-2-yl)ethynyl)pyridine (MR1). 2-Ethynyl-9,9-
dioctylfluorene (4) (0.20 g, 0.48 mmol), 2,5-dibromopyridine (5)
(0.06 g, 0.25 mmol), Pd(PPh3)2Cl2 (0.02 g, 0.028 mmol), and CuI
(0.009 g, 0.03 mmol) were placed in a dried round-bottom flask,
followed by the addition of diisopropylamine (1 mL) and freshly
distilled THF (25 mL) under a nitrogen atmosphere. The mixture was
refluxed 8 h, allowed to cool to room temperature, quenched with a
saturated solution of ammonium chloride (25 mL), extracted with
ethyl acetate (3 × 25 mL), dried over Na2SO4, evaporated to dryness,
and chromatographed on silica gel (70−230 Mesh) using hexanes. The
brown solid thus obtained was recrystallized from deuterated
chloroform and acetonitrile to yield 80 mg (37%) of MR1 as a yellow
solid. M.P. 78−79 °C. FTIR (ATR cm−1): ν 3268, 2923, 2875, 2316,
Received: November 3, 2017
Revised: April 5, 2018
Published: April 5, 2018
2795 DOI: 10.1021/acs.cgd.7b01542
Cryst. Growth Des. 2018, 18, 2795−2803
Crystal Growth & Design
Scheme 1. Synthesis and Numbering for Molecular Rotors MR1 and MR2a
a
Displayed in color code are the 9-octylfluorenyl stators (blue), the polarizable rotators (red), and the acetylenic axles (black). Reagents and
conditions: (i) 1-Bromooctane, KOH, DMSO, (ii) ethynyltrimethylsilane, Pd(PPh3)2Cl2, CuI, DIPA, reflux, (iii) K2CO3, MeOH/ether, rt., (iv)
Pd(PPh3)2Cl2, CuI, DIPA, THF, reflux.
1467, 843, 827, 737, 571, 555. 1H NMR (CDCl3, 500 MHz) δ 8.82 (d,
J = 1.9 Hz, 1H, H-24), 7.84 (dd, J = 8.1, 1.9 Hz, 1H, H-22), 7.72−7.68
(m, 4H, H-4/H-4′/H-5/H-5′), 7.62−7.58 (m, 2H, H-1/H-3), 7.56−
7.52 (m, 3H, H-1′/H-2′/H-3′), 7.36−7.32 (m, 6H, H-6/H-6′/H-7/H-
7′/H-8/H-8′), 1.97 (q, J = 7.7 Hz, 8H, H-10/H-10′), 1.23−1.17 (m,
8H, H-16/H-16′), 1.15−1.02 (m, 32H, H-12/H-12′/H-13/H-13′/H-
15/H-15′), 0.82 (t, J = 7.2 Hz, 12H, H-17/H-17′), 0.61 (br s, 8H, H-
11/H-11′). 13C NMR (CDCl3,125 MHz) δ 152.47 (C-24), 151.18 (C-
9a′), 151.07 (C-9a), 150.88 (C9b′), 150.78 (C-9b), 142.32 (C-4a),
142.13 (C-4a′), 141.92 (C-20), 140.19 (C-4b/C-4b′), 138.30 (C-22),
130.73 (C-3′), 127.76 (C-7), 127.74 (C-7′), 126.92 (C-6′), 126.90 (C-
6), 126.71 (C-1), 126.22 (C-1′), 126.02 (C-21), 122.90 (C-8/C-8′),
120.43 (C-2′), 120.14 (C-5), 120.11 (C-5′), 120.07 (C-2), 119.74 (C-
4), 119.68 (C-4′), 119.44 (C-23), 95.58 (C-18′), 92.52 (C-18), 88.70
(C-19), 86.05 (C-19′), 55.17 (C-9′), 55.14 (C-9), 40.31 (C-10/C-
10′), 31.76 (C-15/C-15′), 30.00 (C-14), 29.98 (C-14′), 29.21 (C-13/
C-13′), 29.20 (C-12/C-12′), 23.72 (C-11′), 23.69 (C-11), 22.57 (C-
16/C-16′), 14.06 (C-17/C-17′). HRMS (APCI-TOF+) m/z: [M+ +
H]+ Observed: 904.6755, required for C67H86N: 904.6754, error: 0.23
ppm
2,5-Bis(9,9-dioctyl-2-ethynyl-fluoren)fluorobenzene (MR2). Syn-
thesized as described above for MR1, from 2-ethynyl-9,9-dioctyl-
fluorene (4) (0.15 g, 0.36 mmol) and 1,4-dibromo-2-fluorobenzene
(6) (0.05 g, 0.18 mmol). The procedure yielded 92 mg (56%) of MR2
as a pale yellow solid (92 mg, 56%). M.P. 116−117 °C. FTIR (ATR,
cm−1) 3063, 2925, 2853, 1467, 1451, 828, 737, 721. 1H NMR (CDCl3,
500 MHz) δ 7.72−7.69 (m, 4H, H-4/H-4′/H-5/H-5′), 7.57−7.51 (m,
5H, H-1/H-1′/H-3/H-3′/H-21), 7.37−7.32 (m, 8H, H-6/H-6′/H-7/
H-7′/H-8/H-8′/H-22/H-24), 1.98 (t, J = 8.3 Hz, 8H, H-10/H-10′),
1.26−1.19 (m, 8H, H-16/H-16′), 1.15−1.05 (m, 32H, H-12/H-12′/
H-13/H-13′/H-14/H-14′/H-15/H-15′), 0.82 (t, J = 7.2 Hz, 12H, H-
17/H-17′), 0.65−0.59 (m, 8H, H-11/H-11′). 13C NMR (CDCl3, 125
MHz) δ 162.09 (d, 1JC‑F = 251.9 Hz, C-25), 151.07 (C-9a), 151.05 (C-
9a′), 150.84 (C-9b′), 150.80 (C-9b), 141.96 (C-4a′), 141.95 (C-4a),
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140.29 (C-4b), 140.25 (C-4b′), 133.18 (d, 3JC‑F = 2.2 Hz, C-21),
130.78 (C-3′), 130.71 (C-3), 127.68 (C-7′), 127.64 (C-7), 127.30 (d,
4
JC‑F = 3.4 Hz, C-22), 126.90 (C-6′), 126.88 (C-6), 126.03 (C-1),
126.01 (C-1′), 124.88 (C-20), 123.01 (C-8), 123.01 (C-8′), 120.80
(C-2), 120.66 (C-2′), 120.07 (C-5/C-5′), 119.68 (d, 3JC‑F = 5.0 Hz, C-
24), 118.39 (C-4), 118.30 (d, 3JC‑F = 22.6 Hz, C-23), 118.21 (C-4′),
97.36 (C-18), 93.34 (C-18′), 88.10 (C-19′), 82.57 (C-19), 55.16 (C-
9′), 55.14 (C-9), 40.33 (C-10/C-10′), 31.78 (C-15/C-15′), 30.00 (C-
14/C-14′), 29.22 (C-12/C-12′/C-13/C-13′), 23.70 (C-11/C-11′),
22.59 (C-16/C-16′) 14.07 (C-17/C-17′). Anal. Calcd for C68H85F: C,
88.64; H, 9.30. Found: C, 88.36; H, 9.62.
2.3. Single X-ray Diffraction Studies. Crystals of MR1 and MR2
suitable for single-crystal X-ray diffraction studies were obtained by
room temperature evaporation of a saturated solution of the analytes
in a chloroform/acetonitrile mixture.
The intensity data were collected on an Enraf-Nonius Kappa
diffractometer with a CCD area detector (λMoKα = 0.71073 Å,
monochromator: graphite) and a Bruker D8 Venture CMOS
diffractometer at 173 K. The crystals were mounted on conventional
MicroLoops. All heavy atoms were found by Fourier map difference
and refined anisotropically. All reflection data sets were corrected for
Lorentz and polarization effects. The first structure solution was
obtained using the SHELXS-2017 program, and the SHELXL-2017
was applied for refinement and output data. 9 All software
manipulations were done under the WinGX environment program
set. The programs Mercury 3.7 and ORTEP-3 were used to prepare
artwork representations.10,11 Free volumes around the rotators were
approximated to the space confined by a hypothetical prism with two
edges defined with the distances shown in Figure 3 (∼8 and ∼10 Å)
and the third edge taken as the C2−C2′ distance (∼11 Å).
2.4. Theoretical Methods. Gas phase geometries were computed
within the framework of the Density Functional Theory using the
Gaussian 09W software package,12 from the crystal structures of MR1
and MR2. Both equilibrium geometries were obtained using the
DOI: 10.1021/acs.cgd.7b01542
Cryst. Growth Des. 2018, 18, 2795−2803
Crystal Growth & Design
Figure 1. Crystal structures of (a) MR1 and (b) MR2 with the thermal ellipsoids drawn at 50% probability for every atom other than hydrogen.
double-ζ 6-31G(d,p) polarized basis set with different hybrid
functionals: B3LYP, PBE0, and the long-range corrected CAM-
B3LYP and M06-2X. In every case, a former optimization at the HF/6-
31G(d,p) was required. These relaxed conformers were confirmed as
energetic local minima through analytical inspection of their
vibrational frequencies and were further optimized using the integral
equation formalism of the Polarizable Continuum Model (IFPCM)
with chloroform as solvent. The resulting geometries were subjected to
a TD-DFT computation of the vertical excitation energies for MR1
and MR2, which were compared to the experimental electronic
spectra. From all the methods, only the CAM-B3LYP and M06-2X
functionals were found to predict these energies accurately, with
differences between the experimental and computed excitations below
the usually accepted threshold of 0.3 eV (Figure S8). These functionals
were consequently employed with Dunning’s cc-pVDZ basis set in the
computation of first-order hyperpolarizabilities (β), as the use of such
larger atomic functions has proved effective in predicting this optical
parameter.13 For consistency reasons, the same method was applied in
the computation of rotational activation energies (Ea) and static
molecular dipoles (μ0). It should be remarked that, throughout the
entire set of computations, the CAM-B3LYP/cc-pVDZ was
unambiguously found as the best DFT method in terms of accuracy
and computational expense. Also, the use of functionals lacking long-
range corrections behaved catastrophically, particularly at predicting
electronic parameters such as electronic excitation energies and should
therefore be avoided when computing NLO parameters of molecules
with similar quadrupolar architectures as the rotors herein studied.
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Evaluation of the modulation of μ0 and β as functions of the
orientation of the pyridine and fluorobenzene rotators was carried out
by varying their relative positions from the coplanar (equilibrium)
geometries. Single-point energy calculations were then performed for
conformers with successive 15° increments in the dihedral angle
formed between the plane containing the rotator and that of the 9-
octyl-fluorenyl stators, i.e., the [C1−C2−C20−C21] torsion angle.
In order to confirm or correct the NMR assignments, a Gaussian
Invariant Atomic Orbital (GIAO) computation of the isotropic
magnetic shieldings of 13C nuclei was performed. These calculations
were conducted at the PBE0/6-31G(d,p) level of theory rather than
with the M06-2X/cc-pVDZ approach, as it was unexpectedly found
that the former predicted the desired 13C chemical shifts with better
accuracy and performance, as reflected in lower Mean Unsigned Errors
(MUE, Table S1) obtained for both MR1 and MR2. Although the
methodology employed provides absolute chemical shifts, for clarity,
they are herein reported as scaled with respect to an external
tetramethylsilane (TMS) reference computed at the B3LYP/6-
311+G(2d,p) level of theory.
3. RESULTS AND DISCUSSION
3.1. Synthesis and Molecular Characterization. Sono-
gashira double cross-coupling reaction between 2-ethynyl-9,9-
dioctylfluorene (4) and either 2,5-dibromopyridine (5) or 1,4-
dibromo-2-fluorobenzene (6) allowed access to unsymmetrical
DOI: 10.1021/acs.cgd.7b01542
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Crystal Growth & Design Article

Table 1. Crystal Structure and Refinement Data

compound MR1 MR2
empirical formula C67H85N C68H85F
formula weight 904.42 921.36
temperature 173 K 173 K
crystal system monoclinic monoclinic
space group P21 P21
a (Å) 12.610(16) 12.48(5)
b (Å) 14.291(18) 14.11(4)
c (Å) 16.78 (2) 16.49(5)
α (deg) 90 90
β (deg) 104.07 (4) 103.2(2)
γ (deg) 90 90
volume (Å)3 2933(6) 2825(16)
Z 2 2
density (g·cm−3) 1.024 1.083
crystal size (mm) 0.1 × 0.1 × 0.2 0.32 × 0.069 × 0.04
θ range (deg) 2.19−28.28 2.70−26.71
index ranges −16 ≤ h ≤ 16, −19 ≤ k ≤ 19, −22 ≤ l ≤ 22 −15 ≤ h ≤ 15, −17 ≤ k ≤ 17, −20 ≤ l ≤ 20
Nref 14556 10915
R (reflections) 0.0537 (8423) 0.0575 (7766)
wR2 (reflections) 0.1385 (14374) 0.1167 (10915)

molecular rotors MR1 and MR2 in moderate yields (Scheme

1).
In the 1H NMR spectrum of MR1, two spin systems could
be readily identified through homonuclear COSY (1H−1H)
2D-NMR spectroscopy. The first coupled nuclei was ascribed
to the pyridine ring, with the characteristic resonance of H-24
appearing as a highly deshielded doublet at δ = 8.82 ppm.
Aromatic hydrogens from the fluorene submolecular fragments
appeared as multiplets, with magnetic inequivalences between
the H-1/H-1′ and H-3/H-3′ nuclei from both fluorenyl stators.
Nonetheless, their signals were successfully assigned owing to
their marked long-range scalar couplings.
Most 13C nuclei were also found to be magnetically
nonequivalent in solution, which was observed as a ubiquitous
splitting of the signals in the 13C NMR spectra of both MR1
and MR2, with chemical shift differences even below 0.05 ppm.
Ambiguity found in the assignment of these resonances was
thus circumvented employing APT and 2D (1H−1H, 1H−13C)
NMR techniques and a Gaussian Invariant Atomic Orbital
(GIAO) calculation of the isotropic 13C chemical shifts for both
molecular rotors at the PBE0/6-31G(d,p) level of theory (for
details, see the Supporting Information, Table S1 and Figures
S9 and S10).
3.2. X-ray Diffraction Studies. Crystals of compounds
MR1 and MR2 suitable for SXRD experiments were grown in
chloroform/acetonitrile at room temperature (Figure 1). Figure 2. Calculated PXRD patterns for MR1 (top) and MR2
Interestingly, despite the replacement of the pyridine nitrogen (bottom).
in MR1 for a C-F moiety in MR2, both compounds crystallized
without solvent in the monoclinic P21 space group, with 2 Remarkably, in spite of the presence of the polar pyridine
molecules per unit cell and with nearly the same cell constants and fluorobenzene rotators, the crystal packing of both MR1
(Table 1). Also, both showed an anti conformation for the two and MR2 is dominated exclusively by weak nonpolar contacts
fluorenyl stators, which lie in close orthogonality to the plane among the alkyl chains of the fluorene stators (for details, see
containing the rotator and the acetylenic axles as evidenced by the Supporting Information, Figure S10). It is worth noting that
the values for the [C1−C2−C20−C21] dihedral angles of such absence of intermolecular interactions involving the
84.6° and 86.2° for MR1 and MR2, respectively. To further rotators may facilitate their rotational dynamics.
evidence the similarities of these isomorphic crystals, a Further analysis of the crystalline structure of these
comparison between their calculated PXRD patterns is depicted compounds revealed that a given rotator has 3.8−5.2 Å of
in Figure 2. distance from the ring centroid to the closest atoms within the
2798 DOI: 10.1021/acs.cgd.7b01542
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Crystal Growth & Design
Figure 3. Distances (Å) from a rotator centroid to the closest atoms within the crystal packing of (a) MR1 and (b) MR2.
crystal lattice of MR1 and MR2 (see Figure 3), conferring a
free volume of ca. 796 and 854 Å3 around the pyridine and
fluorobenzene rotators, respectively, which may be enough to
allow the rotational dynamics of these molecules.3 However,
the distances between the centroids of two adjacent rotators are
of 11.0 and 10.8 Å for MR1 and MR2, respectively, which may
limit correlation of internal rotational motion. Nonetheless,
cooperative effects arising by the alignment of molecular
dipoles throughout the crystallographic c axis (vide inf ra) of
these crystal arrays may help overcome this limitation.
Both MR1 and MR2 crystal structures exhibited intriguing
2D layers that resemble the lipidic bilayers that constitute cell
membranes (Figure 4). This peculiar self-assembly, which
spreads along the crystallographic c axis, is of relevance within
the study of solid-state molecular rotors due to the need (of
that particular type of molecular machines) of having an
amphidynamic character, i.e., to display fast molecular dynamics
while maintaining a highly ordered phase, such as that offered
by a crystalline array. The similarity of the crystal packing of
these studied molecular rotors with the lipidic bilayers in cell
membranes is thus of importance due to the fact that cell
membranes constitute an archetypal example of an amphidy-
namic system, given that they are well-known to present both
phase order and fast molecular dynamics.14
As depicted in Figure 5, both MR1 and MR2 showed a
peculiar orientation of molecular dipoles throughout the
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crystallographic b axis. We expect that, given the free space
that the rotators display and the low rotational energetic
barriers provided by the acetylenic axles, the orientation of
these microscopic molecular dipoles might change with the
presence of an applied magnetic field, yielding these crystalline
systems as molecular analogues of macroscopic compasses.
It is worth noting that, because of their chiral self-assembly,
these isomorphic crystals are also of particular interest for
nonlinear optical (NLO) applications, where noncentrosym-
metric arrangements are required for solid-state applications,
such as the second (or higher order) harmonic generation.
Moreover, due to the alignment of molecular dipoles within the
crystals, these materials are expected to display enhanced NLO
properties due to cooperative effects among the static dipoles
aligned throughout the crystal lattice.
3.3. Theoretical Studies. The molecular structure of rotors
MR1 and MR2 was studied through DFT computations using
the cc-pVDZ basis set with the hybrid long-range corrected
M06-2X and CAM-B3LYP functionals. Negligible geometrical
differences between the gas-phase geometries were found for
both methods. When compared to the solid-state conformers,
the main geometrical difference is that the former are predicted
to have coplanarity among the pyridine (MR1) or fluoroben-
zene (MR2) rotators and the fluorenyl stators (Figure 6). Such
conformations may reasonably be preferred due to a better
stabilization of the static molecular dipoles (μ0) in these planar
DOI: 10.1021/acs.cgd.7b01542
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Crystal Growth & Design Article

Figure 4. Schematic representation of 2D layers formed within the crystal packing of compounds MR1 (top) and MR2 (bottom). The crystal
structures are viewed along the crystallographic b axis, and the rotators are in space-filling representation for clarity.

Figure 5. Orientation of static molecular dipoles along the crystallographic b axis for MR1 (left) and MR2 (right).

geometries. This was confirmed through single-point energy
computation at the same level of theory for both conformers,
showing changes in molecular dipoles (Δμ0) of ca. 0.25 and
0.05 D for MR1 and MR2, respectively, favoring the planar
conformations.
In order to estimate how free the pyridine and fluorobenzene
rotators are to perform the rotational work, the energy profiles
of both MR1 and MR2 were computed for conformers with
incremental 15° deviations from the equilibrium (planar)
geometries, allowing us to predict very small activation energies
(Ea) for both rotors (2.5−4.5 kcal/mol), mainly accounted for
2800
the loss of π-conjugation and aromaticity of these molecules as
they deviate from coplanarity (Figure 7). It is worth noting
that, even considering that the nonplanar solid-state conformers
should have been observed due to potential C−H···π contacts
involving the rotators, these weak (∼1.5 kcal/mol) 15
interactions should not restrain rotational motion in the solid
state, as efficient dynamics have been observed with even higher
energetic thresholds.5
As mentioned earlier, prospective applications of molecular
rotors include their use as microscopic analogues of compasses,
with conformational changes effectively induced by a magnetic
DOI: 10.1021/acs.cgd.7b01542
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Crystal Growth & Design
Figure 6. Superposed equilibrium (M06-2X/cc-pVDZ, orange) and
solid-state (blue) geometries for MR1 (top) and MR2 (bottom).
stimulus. Due to the absence of inversion symmetry in the
crystal packing of MR1 and MR2, a pulsed laser could be used
to induce not only the conformational change but also an
associated even-order nonlinear optical (NLO) response, such
as the Second Harmonic Generation (SHG). These optical
phenomena may arise from a crystal as its molecules polarize
due to the application of an external magnetic field, following16
Figure 7. Energy profiles for the [C1−C2−C20−C21] dihedral angle in MR1 (top) and MR2 (bottom), respectively, using the cc-pVDZ basis set
with the CAM-B3LYP (blue) and M06-2X (red) functionals.
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Pi(E) = αijEj + βijk EjEk + ... (1)
where P(E) is the molecular polarization induced by the electric
field (E), α and β are the molecular polarizability and first-order
hyperpolarizability, respectively, and i, j, k refer to the molecular
coordinate system.
The SHG response in crystals is restricted to non-
centrosymmetric space groups, as the presence of inversion
symmetry within the molecule yields β = 0 and a cancelation of
resonant dipoles is expected in centrosymmetric supra-
molecular arrangements. In noncentrosymmetric media, the
magnitude of β greatly influences the strength of the SHG
signal. This leads to the possibility of developing photonic
switches from MR1 and MR2 where, as consequence of an
induced reorientation of the rotator, a modulation of β and thus
of the SHG response could be achieved. It should be noted
that, because of the quasi-centrosymmetric quadrupolar (D-π-
A-π-D) topology of these molecules, small (but nonzero)
values of β are expected in the coplanar conformations.
Nonetheless, β should be modified as the rotators deviate from
coplanarity, as this process interrupts π-conjugation and
consequently alters the molecular topology, leading to an
“OFF” state (i.e., the conformer with the lowest β) which could
be switched to an “ON” state as molecular dipoles are
reoriented due to the application of an external magnetic field,
as successfully described by our group for analogous systems.17
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Crystal Growth & Design
Figure 8. Modulation of the static dipole moment (μ0, dotted lines) and the first-order hyperpolarizability (β, solid lines) as functions of the [C1−
C2−C20−C21] dihedral angle for MR1 (top) and MR2 (bottom) using the cc-pVDZ basis set with the CAM-B3LYP (blue) and M06-2X (red)
functionals.
The results of a DFT computation of the modulation of μ0
and β as functions of the orientation of the fluorobenzene and
pyridine rotators are depicted in Figure 8. Surprisingly, while
the variation of μ0 followed the same trend in both rotors
(increasing as the molecule deviates from coplanarity and thus
of centrosymmetry), opposite behaviors were found for the
modulation of β. In the case of MR1, β has a minimum value at
a dihedral angle of 0° (i.e., in the coplanar conformer) and a
maximum near 90°, as expected for the change in topology
previously explained. Strikingly, both DFT methods employed
predicted the exact opposite trend for MR2 with a maximum
value of β at coplanarity, which markedly decreases as the
dihedral angle approaches 90°.
The rationale behind this divergent behavior is far from
trivial and out of the scope of this paper. Further studies should
deal with computing the involved excited states, since the value
of β, commonly assumed by a two-state model,18 depends not
only on the herein studied ground state dipole (μg) but also on
the change in dipole moment between the involved eigenstates
(Δμge) and on the energy (Ege) and oscillator strength ( fge) for
the transition, following
Δμge fge 2
β∝
Ege 2
Despite the different behaviors of both molecular rotors,
ON/OFF ratios of 2.6−2.9 for MR1 and 1.3−1.4 for MR2 are
expected, according to DFT computations. While the
Article
computed values are not particularly appealing at the molecular
level, an enhancement in the NLO response in these crystals
may occur due to cooperative effects caused by the crystal
packing as mentioned earlier (vide supra).
4. CONCLUSIONS
Two molecular rotors featuring 9-octylfluorenyl stators with
pyridine or fluorobenzene rings as rotators were successfully
obtained employing a Sonogashira double cross-coupling
reaction as the key synthetic step. The crystal structure of
these compounds formed 2D layers that highly resemble cell
membranes, which suggests these crystals may also display a
dynamic behavior within a highly ordered phase. Free volumes
of ca. 796−854 Å3 were estimated around the rotators,
potentially allowing their rotational dynamics in the solid
state, which may occur at room temperature according to DFT
computations. Moreover, both their chiral crystal packing and
the modulation of the first-order hyperpolarizabilites (β) with
the orientation of the rotators make these compounds
particularly appealing as photonic switches, which may
reorientate upon the application of a magnetic field, potentially
displaying rotational work such as that of a gyroscope. In silico
evaluation of the modulation of β as a function of the rotational
(2) dynamics showed ON/OFF ratios of ∼2.7 and ∼1.3, further
confirming a prospective application as photonic switches. The
experimental evaluation of the solid state rotational dynamics of
deuterated isotopologues, as well as the study of the nonlinear
optical behavior of these materials, are ongoing.
2802 DOI: 10.1021/acs.cgd.7b01542
Cryst. Growth Des. 2018, 18, 2795−2803
Crystal Growth & Design
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.7b01542.
Synthesis of starting materials, 1H, 13C NMR, and HRMS
spectra, elemental analyses, crystal packing, optimized
geometries and Gaussian Invariant Atomic Orbital 13C
chemical shifts plots (DFT), as well as crystal packing of
MR1 and MR2 (PDF)
Accession Codes
CCDC 1582960 and 1582963 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: rsantill@cinvestav.mx.
ORCID
Pablo Labra-Vázquez: 0000-0002-8843-9709
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge support from PAPIIT (IN-216616)
and CONACYT for a doctoral scholarship for P.L.-V (337958).
Marco A. Leyva, Geiser Cuellar, and Teresa Cortez-Picasso
(CINVESTAV-IPN) are gratefully acknowledged for X-ray
structure determinations, HRMS analyses, and NMR experi-
ments, correspondingly. We would like to express our gratitude
to Prof. Pascal G. Lacroix (CNRS) for his valuable comments
on this work.
■
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DOI: 10.1021/acs.cgd.7b01542
Cryst. Growth Des. 2018, 18, 2795−2803