Article

pubs.acs.org/Organometallics

Functionalized Ruthenium Dialkynyl Complexes with High Second-

Order Nonlinear Optical Properties and Good Potential as Dye
Sensitizers for Solar Cells
Filippo Nisic,† Alessia Colombo,*,† Claudia Dragonetti,†,‡ Eleonora Garoni,† Daniele Marinotto,‡
Stefania Righetto,† Filippo De Angelis,*,§ Maria Grazia Lobello,§ Paolo Salvatori,§ Paolo Biagini,*,∥
and Fabio Melchiorre∥
†
Dipartimento di Chimica dell’Università degli Studi di Milano, UdR-INSTM, and ‡ISTM-CNR, via Golgi 19, I-20133, Milano, Italy
§
Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), Istituto CNR di Scienze e Tecnologie Molecolari, Via Elce
di Sotto 8, I-06213, Perugia, Italy
∥
Centro Ricerche per le Energie non Convenzionali, Istituto eni Donegani, via G. Fauser 4, 28100, Novara, Italy
*
S Supporting Information

ABSTRACT: Various dipolar π-delocalized Ru(II) dialkynyl

complexes were prepared and characterized. Their second-
order nonlinear optical (NLO) properties were investigated by
the electric-field-induced second harmonic generation
(EFISH) technique working in CH2Cl2 solution with an
incident wavelength of 1907 nm, whereas the dipole moments
were determined by density functional theory (DFT)
calculations. All the investigated complexes are characterized
by a negative value of μβ1.907 EFISH, in agreement with a
negative value of Δμeg (difference of the dipole moment in the
excited and ground state) upon excitation. Their second-order
NLO response can be easily modulated by the nature of the alkynyl substituents. Besides, the most promising “push−pull”
ruthenium diacetylide complex, adequately functionalized for anchoring to TiO2, was tested as photosensitizer in dye-sensitized
solar cells (DSSCs).

■ INTRODUCTION
Compounds with second-order nonlinear optical (NLO)
redox properties which afford the possibility of NLO
switching.15 Ruthenium σ-acetylides have been largely studied
properties are of great interest as molecular building block through hyper-Rayleigh (HRS) scattering measurements, but,
materials for optical communications, optical data processing to our knowledge, only in two cases through electric field
and storage, or electrooptical devices.1 Among them, organo- second harmonic generation (EFISH) measurements.16,17
metallic complexes represent a fascinating and growing class of Thus, a few years ago, an EFISH study showed that dipolar
second-order NLO chromophores that can offer additional alkynyl ruthenium complexes with a phenyleneethynylene or
flexibility, when compared to organic chromophores, due to the phenylenevinylene bridge between a donor “ClRu” moiety and
presence of metal−ligand charge-transfer transitions usually at a nitro acceptor group, such as trans-[Ru(4,4′-CCC6H4C
relatively low energy and of high intensity, tunable by virtue of CC6H4NO2)Cl(dppe)2] (dppe = Ph2PCH2CH2PPh2) and
the nature, oxidation state, and coordination sphere of the trans-[Ru{(E)-4,4′,4″-CCC6H4CCC6H4CH
metal center.1−6 CHC6H4NO2}Cl(dppm)2] (dppm = Ph2PCH2PPh2), are
In particular, metal σ-acetylides constitute a widely characterized by good second-order NLO properties.16 Also,
investigated class of second-order NLO chromophores, mainly very recently, some of us reported that a dinuclear Ru(II)
developed by Humphrey et al.,7−9 where the metal acts as the complex, where two “phenylalkynyl-Ru” moieties are separated
donor group of a Donor-Acceptor system connected by a π- by a bridge consisting of 2,1,3-benzothiadiazole (BTD) flanked
linker. The almost linear M-CC-R structure allows a good on either side by 2,5-thienyl units (Th), is characterized by an
coupling between the d metal orbitals and the π* system of the unexpected high EFISH NLO response where the benzothia-
σ-acetylide bridge, affording a significant NLO response diazole moiety acts as an acceptor.17 These observations
controlled by low-energy MLCT excitations. Ruthenium σ- prompted us to prepare novel dipolar mononuclear ruthenium
alkynyl complexes are very attractive, due to their facile high-
yielding syntheses,10,11 enhanced NLO coefficients,12,13 easy Received: September 11, 2014
construction of multimetallic dendrimers,14 and reversible

© XXXX American Chemical Society A DOI: 10.1021/om5009378

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Chart 1. Structure of the Investigated Ru(II) Complexes

Scheme 1a

a
(i) Trimethylsilylacetilene, Pd(PPh3)2Cl2, CuI, PPh3, TEA, 70 °C, 16 h, 80%; (ii) K2CO3, MeOH/THF, 24 h, 90%; (iii) trans-[ClRu(dppe)2C
CPh], TEA, NaPF6, CH2Cl2, rt, 20 h, 85%; (iv) CNCH2COOMe, piperidine, MeOH, 50°C, 3 h, 98%; (v) K2CO3, MeOH/THF,40 °C, 3 h, 90%;
(vi) trans-[ClRu(dppe)2CCPh], TEA, NaPF6, CH2Cl2, rt, 20 h, 70%.

dialkynyl complexes (Chart 1) and to study their second-order and the optical properties were evaluated by density functional
NLO properties, using the EFISH technique, in order to get a theory (DFT) calculations.
But, thanks to the linear geometry of the alkynyl unit and its
better understanding of the 2,1,3-benzothiadiazole as acceptor
π-unsaturated character, metal alkynyls are attractive building
moiety and to investigate new “Donor-phenylalkynyl-Ru- blocks not only for the preparation of materials with optical
alkynylphenyl-Acceptor” architectures. The dipole moments nonlinearity but also for molecular wires and polymeric
B DOI: 10.1021/om5009378
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Scheme 2a

a
(i) tBuO−K+, THF, rt, 16 h, 80%; (ii) trimethylsilylacetilene, Pd(PPh3)2Cl2, CuI, PPh3, TEA, 70 °C, 16 h, 60%; (iii) K2CO3/MeOH, 24 h (95%).

Scheme 3a

a
(i) trans-[Ru(dppe)2Cl2], NaPF6, CH2Cl2, 40 °C 24 h, TEA, rt, 24 h 85%; (ii) p-ethynyl-benzaldehyde, NaPF6, TEA, CH2Cl2, rt, 24 h 90%; (iii)
CNCH2COOCH3, piperidine, CH2Cl2, rt, 18 h, 90%.

organometallic materials, which can possess interesting proper- A and B were synthesized according to the simple synthetic
ties such as luminescence, liquid crystallinity, and electrical strategy reported in Scheme 1: the starting materials trans-
conductivity.18 Metal−alkynyl complexes have been readily Ru(dppe)2Cl2 and 4-(5-bromothiophen-2-yl)-7-(thiophen-2-
employed as simple electronic components with the ability to yl)benzo[c][1,2,5]thiadiazole derivatives 1 and 2 were synthe-
transport electronic charges between two points, allowing the sized following reported methods.35 A and B were obtained
study of intramolecular charge-transport mechanisms over long using an adaptation of the method of Humphrey et al.,36 by
distances.19−21 The ability of ruthenium to operate as a reaction of the known [ClRu(dppe)2CCPh]37 with the
connector allowing electron flow to occur between different deprotected alkyne-derivative of 3 and with 5. F, similar to B
elements in trans-ditopic architectures was demonstrated,22−25 but with a carboxylic acid function instead of the methyl ester,
and its exceptional propensity to serve as efficient electron was prepared starting from the potassium salt derivative of 5;
relays in nanoscale oligomeric structures was reported.26−29 final acidification of the potassium salt of B with trifluoroacetic
Metal alkynyls also showed their potential as donor acid gave F.
components of bulk heterojunction solar cells.30−34 In order to obtain C and D, we first prepare the acetylene
We asked ourselves whether the trans-ruthenium diacetylide derivative 10 as reported in Scheme 2; it was then reacted with
motif could act as an efficient relay within a “push−pull” trans-[Ru(dppe)2Cl2] as described in Scheme 3.
architecture such as that of the new complex D and, therefore, The 4-ethynyl-benzaldehyde was prepared according to the
could find application in the field of DSSCs. For this reason, we literature,38 whereas (E)-4-(4-ethynylstyryl)-N,N-diphenyl-
prepared the related complex E bearing a carboxylic acid aniline 10 was synthesized as reported in Scheme 2. The
anchoring group instead of the methyl ester function and trans isomer 8 was obtained by Horner−Hammonds reaction
studied in a preliminary way its potential as dye sensitizer for between 4-diphenyl-amminobenzaldehyde 6 and the phospo-
solar cells. For comparison, F, the carboxylic acid derivative of nate 7.
B, was also investigated.

■
The synthesis of the desired complexes C and D was
accomplished by using terminal alkyne activation by ruthenium
RESULTS AND DISCUSSION complexes,39 thereby providing selective formation of vinyl-
Synthesis. Various novel ruthenium acetylide complexes idene complexes that are the key intermediates for the
(Chart 1) were prepared following the synthetic pathways formation of monoalkynyl complex 11 (by deprotonation
shown in Schemes 1−3. with TEA) and unsymmetric bis-alkynyl complex 12 (by
C DOI: 10.1021/om5009378
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Figure 1. Optimized geometries of complexes A−D.

Table 1. Electronic Spectra, μβ1.907 EFISH, μ, and β1.907 EFISH of the Investigated Ru(II) Complexes
complex absorbancea λmax/nm [ε/M−1 cm−1] μβ1.907 EFISHb (×10−48) esu μc (×10−18) esu β1.907 EFISHd,g (×10−30) esu
A 365 [36200], 489 [31400] −1550 6.9 −225
Be 397 [28400], 497 [64400] −1700 18.1 −94
C 289 [5600], 427 [9800] −345 5.9 −58
Df 399 [21500], 437 [16300] −780 7.9 −99
a
In CH2Cl2. bWorking in CH2Cl2 10−3 M with an incident radiation wavelength of 1.907 μm; the error is 10%. cCalculated at the B3LYP level in
CH2Cl2; in vacuo, μ = 5.7, 13.54, 4.4, and 6.0 × 10−18 esu for complexes A, B, C, and D, respectively. At the CAM-B3LYP level, μ values are slightly
lower; see the Supporting Information. dBy using μ calculated in CH2Cl2; by using μ calculated in vacuo, β1.907 EFISH = −272, −126, −78, and −130
× 10−30 esu for complexes A, B, C, and D, respectively. At the CAM-B3LYP level; see the Supporting Information. eFor complex F: λ (nm) [ε (M−1
cm−1)] = 395 [22500], 493 [59600]. fFor complex E: λ (nm) [ε (M−1 cm−1)] = 267 [17900], 428 [10700]. gβ0 values are reported in Table S12 in
the Supporting Information.

introduction of a second alkynyl moiety at the ruthenium between the phenyl and the thiophene planes. Similarly to B,
center of the monoalkynyl complex). complexes C−D show a dihedral angle of about 60° between
[RuCl(dppe) 2 ][PF 6 ] was generated from trans-[Ru- the donor and the acceptor groups.
(dppe)2Cl2] by chloride abstraction using sodium hexafluo- The absorption maxima of the four complexes are reported
phosphate and subsequently treated with the stoichiometric in Table 1. TD-DFT calculations, by using two different
amount of (E)-4-(4-ethynylstyryl)-N,N-diphenylaniline 10 and exchange-correlation functionals, have been performed to gain
TEA in order to form the monoalkynyl complex trans-[Ru(C information on the spectral features of the considered
C-4-(E)-ethynylstyryl-N,N-diphenylaniline)Cl(dppe)2] 11. compounds. The B3LYP functional underestimates the λmax,
Using an analogous approach, the substitution of the in a range between 0.30 and 1.25 eV, for all the considered
remaining chloride ligand of 11 with 4-ethynylbenzaldehyde compounds. On the other hand, by considering a rigid shift of
afforded C; subsequent condensation with methyl cyanoacetate the excitation energies, a well-balanced description of the whole
in the presence of piperidine gave the target complex D in good spectra, both in terms of energies and intensities, is obtained.
yields. E was obtained in a similar manner by Knoevenagel The CAM-B3LYP functional better performs for complexes A
condensation between C and cyanoacetic acid. and B, where a longer intramolecular charge transfer occur,
The molecular structures of the new compounds were while, for C and D, the calculated excitation energies are
characterized by using 1H NMR and mass spectroscopy. overestimated by about 0.4 eV. A detailed list of the calculated
Optimized Geometry, Optical Properties, and Sec- excitation energies is reported in the Supporting Information.
ond-Order NLO Measurements. In Figure 1, we report the In all cases, the absorption band in the visible region is mainly
optimized geometry in vacuum of A−D. Complex A is characterized by HOMO (highest occupied molecular
characterized by a quite planar arrangement of the donor- orbital)−LUMO (lowest unoccupied molecular orbital) tran-
metal-acceptor backbone. The insertion of the hexyl chains on sitions, with some contribution of the lower occupied molecular
the thiophene moieties causes an increase of the dihedral angle orbitals (HOMO-1/HOMO-2). The HOMOs of all the
D DOI: 10.1021/om5009378
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Figure 2. Schematic representation of the energy levels of complexes A−D. Isodensity surface plots (isodensity contour: 0.035) of HOMO and
LUMO molecular orbitals are also shown.

investigated complexes are Ru orbitals combined with the π value (−900 × 10−48 esu) was also reported for the related
orbitals of thiophene and benzothiadiazole groups (complexes dinuclear complex [Ph-CC-Ru(dppe)2-CC-Th-BTD-Th-
A−B) or of the (E)-4-(4-ethynylstyryl)-N,N-diphenylaniline CC-Ru(dppe2)-CC-Ph] (BTD = 2,1,3-benzothiadiazole;
(complexes C−D). The lowest unoccupied molecular orbitals Th = 2,5-thienyl),17 but A has a much higher absolute value of
(LUMOs) are instead completely localized on the acceptor μβ1.907 EFISH (−1550 × 10−48 esu) due to a much higher dipole
moieties without any contribution from the metal (Figure 2). In moment in the ground state (μ of complex A is 6.9 × 10−18 esu,
particular, for complexes A−B, LUMO is strongly stabilized, whereas μ of [Ph-CC-Ru(dppe)2-CC-Th-BTD-Th-CC-
due to the delocalization on the thiophene and benzothiadia- Ru(dppe2)-CC-Ph]17 is 1.6 × 10−18 esu) . The value
zole groups. The presence of the methyl-cyanoacrylate moieties determined for B (−1700 × 10−48 esu) is even higher due to a
on the acceptor part of the complexes (complexes B−D) causes large increase of the dipole moment, attributed to the
a further stabilization of the LUMO orbital. functionalization of the thienyl end-group with a methylcya-
In order to investigate their second-order NLO properties, noacetate moiety, although the absolute value of β1.907 EFISH is
the various ruthenium(II) complexes were investigated by the lower (Table 1). The simple complex C with a “Donor-
EFISH technique (see Table 1). It is known that this phenylalkynyl-Ru-alkynylphenyl-Acceptor” architecture (Donor
technique40−42 can provide direct information on the intrinsic = Ph2NPhCHCH; Acceptor = CHO; see Chart 1) is
molecular NLO properties through eq 1 characterized by the lowest β1.907 EFISH, in agreement with the
γEFISH = (μβEFISH /5kT ) + γ( −2ω; ω , ω , 0) particularly high HOMO−LUMO gap (Figure 2),5 which
(1) increases by a factor of 2.3 upon substitution of the aldehyde
where μβEFISH/5kT is the dipolar orientational contribution and function by the more electron-withdrawing methylcyanoacetate
γ(−2ω; ω, ω, 0), a third-order term at frequency ω of the moiety (D) due to an increase of both μ and β1.907 EFISH. It is
incident light, is a purely electronic cubic contribution to γEFISH worth pointing out that the μβ1.907 EFISH value of B is more than
which can usually be neglected when studying the second-order twice that of D, but this is due to a much higher dipole
NLO properties of dipolar compounds.5 moment, the quadratic hyperpolarizability of both complexes
In Table 1 are reported the μβ1.907 EFISH values of all the being similar. Remarkably, A is characterized by the highest
investigated complexes, measured in CH2Cl2 solution with an β1.907 EFISH value (−225 × 10 −30 esu) reported for a
incident wavelength of 1.907 μm. To obtain β1.907 EFISH, the mononuclear alkynyl ruthenium complex,16 in agreement with
projection along the dipole moment axis of the vectorial a quite planar arrangement of the donor-metal-acceptor
component of the tensor of the quadratic hyperpolarizability, it backbone (Figure 1) and a low HOMO−LUMO gap (Figure
is necessary to know the dipole moment, μ. In the present 2). Calculation of the dipole moments with the CAM-B3LYP
study, we used the theoretical dipole moments calculated as functional provides slightly lower values of μ, and consequently
described in the Experimental Section (see also the Supporting higher β1.907 EFISH (see the Supporting Information). No
Information). significant differences were observed along the series of
All the novel investigated complexes are characterized by a investigated complexes, making us confident about the
negative value of μβ1.907 EFISH, in agreement with a negative employed computational setup.
value of Δμeg (difference of the dipole moment in the excited Complexes E and F in DSSCs. Photoelectrochemical cells,
and ground state) upon excitation.5 A negative μβ1.907 EFISH capable of directly converting sunlight into electrical power, are
E DOI: 10.1021/om5009378
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Organometallics Article

one of the most promising devices in the search for sustainable Table 2. Main Photovoltaic Parametersa,b of DSSCs Based
and renewable sources of clean energy. Dye-sensitized solar on Complexes E and F, in Comparison with Those Based on
cells (DSSCs)43−52 are considered a realistic solution for the Ruthenium Benchmark N719
harnessing the energy of the sun and converting it into
dye area/cm2 Jsc/mA cm−2 Voc/mV FF η/%
electrical energy, with power conversion efficiencies now
exceeding the value of 12.3%.53 E 0.0979 4.6 578 56.1 1.5
Solar light harvesting is the most important step of the F 0.0898 1.5 432 46.5 0.3
photovoltaic process; consequently, the photosensitizer plays a N719 0.1025 15.2 745 71.9 8.1
a
key role in DSSCs. It might be characterized by an absorption By using a black mask (0.1672 cm2). bElectrolyte composition: 0.6 M
spectrum that spans the entire visible range and extends into N-methyl-N-butylimidazolium iodide, 0.04 M iodine, 0.025 M LiI, 0.05
the near-IR region with a sufficiently high molar absorption M guanidinium thiocyanate, 0.28 M tert-butylpyridine in 15/85 (v/v)
coefficient. Moreover, the HOMO/LUMO energies of the dye mixture of valeronitrile/acetonitrile.
must fit the conduction band of the photoanode semiconductor
and the redox couple Nerst potential, in order to provide cm2) and photovoltage levels are coherent with a poor charge
efficient charge transfer mechanisms. Ruthenium based transfer process.
coordination compounds bearing polypyridine ligands such as A much better efficiency was obtained with E (η = 1.5%),
cis-di(thiocyanato)bis(2,2′-bipyridine-4,4′-dicarboxylate)Ru(II) although it does not reach a high value, as expected on the basis
(N354,55 and N71956,57) are among the most studied and of its absorption spectrum (Table 1), which makes it capable to
performing photosensitizers. However, a serious drawback of harvest only a little fraction of the sunlight. Moreover, the value
such Ru(II) complexes is the presence of the anionic measured in the IPCE curve (Figure 3), which does not exceed
thiocyanate ligands which can be easily replaced, in working 20% in the visible region, suggests that, in this case, charge
conditions, by other ligands which generally are contained, in recombinations are very favorable processes and the attempt to
high concentration, into the electrolyte solution, yielding a mitigate them by employing 3 equiv of deoxycolic acid as
decrease of the efficiency during the lifetime of the device.58 coadsorbent does not lead to satisfactory results; in fact, the
Therefore, a lot of efforts have been devoted to the preparation corresponding device shows, under the same conditions, an
of thiocyanate-free ruthenium complexes for DSSCs.59−69 overall power conversion efficiency of 0.8%.
Following our work on the use of diruthenium alkynyl These results, together with those recently published by Tian
complexes, as donor components of bulk heterojunction solar and co-workers72−74 on platinum diacetylide compounds and
cells,34 we anticipated that the trans-ruthenium diacetylide by Olivier et al.75 on analogous ruthenium derivatives, show
motif of B and D might act as an efficient relay within a “push− that it would be correct to propose D-π-M-π-A structured metal
pull” architecture and, therefore, could find application in the acetylide complexes as sensitizers for DSSCs with the aim to
field of DSSCs. For this reason, we prepared two new trans- obtain the right compromise between the best efficiency
diacetylide ruthenium compounds, E and F, both bearing the together with a satisfactory stability. However, our results
required cyano acrylic acid anchoring group, and we studied, in would indicate that, in such organometallic structures, the
a preliminary way, their potentiality as dye sensitizers for solar introduction of selected functional groups along the push−pull
cells.70 The UV−vis spectra of E and F in dichloromethane chain is a very subtle choice and seems to be crucial to obtain
solution show two main absorption bands at 267 nm (ε = 17 good efficiencies in DSSCs; in fact, by simple chemical changes
900 M−1 cm−1), 428 nm (ε = 10 700 M−1cm−1) and 395 nm (ε in the donor moiety of the organometallic dye (introduction of
= 22 500 M−1 cm−1), 493 (ε = 59 600 M−1 cm−1), respectively. a carbazole unit instead of a triphenylamine and removal of the
It should be pointed out that the introduction of a carboxylic styryl moiety), Olivier et al.75 were able to overcome an overall
acid group produces a noticeable lowering of the ε values and a power conversion efficiency of 7%, outperforming fully organic
slight blue shift of the absorption band (Table 1; compare E dyes of analogous structure. The main cause of the higher
and F with D and B) with respect to those measured for the photovoltaic performance of their ruthenium sensitizer,
corresponding methyl ester derivatives, D and B. compared to our complex E, can be highlighted in the better
Complex F shows a LUMO level of −3.43 eV, very similar to light harvesting ability (λmax of 520 nm, with an ε value of 30
the methyl ester analogue, suggesting an unfavorable energy 200 M−1 cm−1). This difference in the absorption spectrum is
level alignment with the TiO2 conduction band edge for the readily converted in a remarkable increase in the photocurrent
electron injection. Similar LUMO values were found, at the value, reaching comparable levels with the standard N719
same calculation level, for another class of sensitizers for which ruthenium dye.
an inefficient electron injection process was highlighted as the
main cause for the low photovoltaic performances.71 On the
other hand, the LUMO level of E (−2.78 eV) appears to be
■ CONCLUSION
In summary, ruthenium(II) dialkynyl complexes are fascinating
adequate to allow the electron injection into TiO2 conduction second-order NLO chromophores whose NLO response can be
band. easily modulated by the nature of the alkynyl substituents, as
The main photovoltaic parameters of E and F are listed in confirmed by the electric-field-induced second harmonic
Table 2, and they are compared, under the same experimental generation technique. Remarkably, A and B, bearing a 2,1,3-
conditions, with those of the benchmark ruthenium dye N719. benzothiadiazole flanked on either side by 2,5-thienyl units, are
As predicted from our theoretical calculations, F fails to act as characterized by the largest values of μβ1.907 EFISH ever reported
a good dye sensitizer. The very low overall power conversion for alkynyl metal complexes and among the best reported for
efficiency observed (0.3%, Table 2) could be ascribed to the organometallic complexes.2−6 They are excellent candidates for
incorrect matching of the energetic levels between the dye and the preparation of second harmonic generation active
TiO2 which practically impedes the passage of the electrons in polymeric films.76,77 In addition, π-delocalized “push−pull”
the device. In fact, the low short-circuit photocurrent (1.5 mA/ ruthenium diacetylide complexes, where a donor and an
F DOI: 10.1021/om5009378
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Figure 3. JV and IPCE curve for E measured in the conditions of Table 2.

acceptor units are separated by the metallic center, exhibit a 4 was prepared starting from the bromo derivative 2 (121.5 mg).
promising application for the next generation of dye-sensitized The crude product was purified using hexane/acetate 8:2 as eluent,
solar cells. affording the product as a red power in 78% yield.

■
1
H NMR (400 MHz, CDCl3, δ (ppm)) 1H NMR (400 MHz,
CDCl3, δ (ppm)) 10.01 (s, 1H), 8.08 (s, 1H), 7.98 (d, J = 7.7 Hz, 1H),
EXPERIMENTAL SECTION 7.95 (s, 1H), 7.87 (d, J = 7.7 Hz, 1H), 3.05 (t, J = 7.6 Hz, 2H), 2.78 (t,
General Comments. Solvents were dried by standard procedures: J = 7.6 Hz, 2 H), 1.83−1.66 (m, 4H), 1.42−1.35 (m, 12H), 0.92−
THF freshly distilled from Na/benzophenone under a nitrogen 0.91(m, 6H), 0.30 (s, 9H).
atmosphere; N,N-dimethylformamide (DMF) was dried over activated MS (FAB+) calcd for C32H40N2OS3Si m/z 592.21, found 592. Anal.
molecular sieves; toluene was distilled over Na/benzophenone, and Calcd: C, 64.82; H, 6.80; N, 4.72. Found: C, 64.89; H, 6.79; N, 4.73.
triethylamine (Et3N) freshly distilled over KOH. All reagents were Synthesis of Derivative 5. To a solution of 4 (67.4 mg, 0.11 mmol)
purchased from Sigma-Aldrich and were used without further and methyl cyanoacetate (12 μL 0.125 mmol) in MeOH (5 mL) was
purification. Reactions requiring anhydrous conditions were performed added piperidine (13 μL, 0.55 mmol). After stirring at 50 °C for 3 h
under nitrogen. 1H and 13C NMR spectra were recorded at 400 MHz and overnight at room temperature, the solvent was removed under
on a Bruker AVANCE-400 instrument. Chemical shifts (δ) for 1H and reduced pressure. The residue was purified by flash chromatography
13
C spectra are expressed in ppm relative to internal Me4Si as standard. on silica gel (hexane/ethyl acetate 95:5). 1H NMR (400 MHz, CDCl3,
Signals were abbreviated as s, singlet; bs, broad singlet; d, doublet; t, δ (ppm)) 8.50 (s, 1H), 8.22 (s, 1H), 8.03 (d, J = 7.8 Hz, 1H), 7.95 (s,
triplet; q, quartet; m, multiplet. Mass spectra were obtained with an 1H), 7.86 (d, J = 7.8 Hz, 1H), 2.93−2.91 (m, 2H), 2.80−2.76 (m,
FT-ICR Mass Spectrometer APEX II & Xmass software (Bruker 2H), 1.74−1.55 (m, 6H), 1.35−1.27 (m, 10H), 0.94−0.91 (m, 6H),
Daltonics) - 4.7 Magnet and Autospec Fission Spectrometer (FAB 0.30 (s, 9H).
ionization). MALDI-TOF mass spectra were obtained using a 50.0 mg (0.83 mmol) of alkyne was deprotected with K2CO3 (126
MICROFLEX-LT (BRUKER) with trans-2-[3-(4-tert-butylphenyl)-2- mg, 0.91 mmol) in THF/MeOH (1:1) 6 mL at r.t for 1 h. The solvent
methyl-2-propenylidene] malononitrile (DCTB) as matrix. Samples was removed under reduced pressure, and the residue was purified by
for MALDI: 1 μL of complex solution + 49 μL of matrix solution + 0.5 flash chromathography on silica gel (hexane/ethyl acetate 95:5). The
μL of LiCl solution + 200 μL of CH2Cl2. The solutions were prepared product was obtained as a dark-red powder in 90% yield. 1H NMR
as follows: 1 mg/mL in CH2Cl2 for the complex, 10 mg of DCTB/mL (400 MHz, CDCl3, δ (ppm)) 8.51 (s, 1H), 8.22 (s, 1H), 8.03 (d, J =
for the matrix solution, and 10 mg of LiCl/mL in methanol for the salt 7.8 Hz, 1H), 7.96 (s, 1H), 7.84 (d, J = 7.8 Hz, 1H), 3.98 (s, 3H), 3.63
solution. (s, 1H), 2.93−2.91 (m, 2H), 2.80−2.76 (m, 2H), 1.74−1.55 (m, 6H),
Electronic absorption spectra were obtained using a Jasco V-530 1.35−1.27 (m, 10H), 0.93−0.91 (m, 6H).
spectrophotometer. MS (FAB+) calcd for C33H35N3O2S3 m/z 601.19, found 601. Anal.
Thin-layer chromatography (TLC) was carried out with precoated Calcd: C, 65.86; H, 5.86; N, 6.98. Found: C, 65.90; H, 5.87; N, 6.96.
Merck F254 silica gel plates. Flash chromatography (FC) was carried Synthesis of Complexes A and B: General Procedure. A mixture of
out with Macherey-Nagel silica gel 60 (230−400 mesh). alkyne (0.07 mmol), trans-[Ru(dppe)2Cl2] (79.7 mg, 0.077 mmol),
Synthesis of Complexes A and B (see Scheme 1 in Results and NaPF6 (26.9 mg, 0.16 mmol) in CH2Cl2 (35 mL) was stirred in
and Discussion). Synthesis of Derivatives 3 and 4. Under a
nitrogen atmosphere, ethynyltrimethylsilane (33 μL, 0.23 mmol) was the dark for 18 h; triethylamine (45 μL) was added and stirring was
added to a degassed solution of the opportune bromo-derivative 1 or 2 maintained for 3h. The solvent was removed under reduced pressure,
(0.21 mmol), [PdCl2(PPh3)2] (4.0 mg, 0.02 mmol), CuI (2.0 mg, 0.04 and the residue was taken up in CH2Cl2 and purified by column
mmol), and PPh3 (2.0 mg, 0.02 mmol) in THF/triethylamine (12 mL, chromatography on neutral alumina.
1/2 v/v). The mixture was stirred for 20 h at 70 °C, and then the Complex A was prepared starting from the free alkyne 4-(5-
solvent was removed under reduced pressure. The residue was ethynylthiophen-2-yl)-7-(thiophen-2-yl)benzo[c][1,2,5]thiadiazole
dissolved in dichloromethane and washed with water. The organic (22.7 mg) obtained from 3 by deprotection with K2CO3 in THF/
layer was dried over Na2SO4, and the solvent was removed at reduce MeOH as described in the synthesis of 5.
pressure. The crude product was purified by flash chromatography on
1
H NMR (400 MHz, CD2Cl2, δ (ppm)) 8.16 (m, 1H), 8.12 (d, J =
silica gel. 4.8 Hz, 1H), 8.08 (d, J = 5.4 Hz, 1H), 7.98 (d, J = 5.4 Hz, 1H), 7.88
3 was prepared starting from 4-(5-bromothiophen-2-yl)-7-(thio- (d, J = 4.8 Hz, 1H), 7.31−7.00 (m, 47H), 2.67 (m, 8H).
phen-2-yl)benzo[c][1,2,5]thiadiazole (79.4 mg). The crude product MS (MALDI-TOF, 2-[(2E)-3-(4-tert-butylphenyl)-2 methylprop-2-
was purified using hexane/acetate 9:1 as eluent, affording the desired enylidene]malonitrile as the matrix) calcd for C76H60N2P4RuS3 m/z
product as a red powder in 80% yield. 1322,19 found 1323. Anal. Calcd: C, 69.02; H, 4.57; N, 2.12. Found:
1
H NMR (400 MHz, CDCl3, δ (ppm)) 1H NMR (400 MHz, C, 69.06; H, 4.55; N, 2.12.
CDCl3, δ (ppm)) 8.15 (d, J = 3.8 Hz, 1H), 8.00 (d, J = 3.8 Hz, 1H), Complex B was prepared starting from the free alkyne 5 (42.13
7.88 (d, J = 7.6 Hz, 1H), 7.86 (d, J = 7.6 Hz, 1H), 7.49 (d, J = 4.8 Hz, mg).
1H), 7.32 (d, J = 3.8 Hz, 1H), 7.23 (t, J = 4.6 Hz, 1H), 0.30 (s, 9H). Elution with hexane/ethyl acetate 8:2 gave a purple band that was
MS (FAB+) calcd for C19H16N2S3Si m/z 396.02, found 396. Anal. collected and dried in vacuo, affording the desired product in 75%
Calcd: C, 57.54; H, 4.07; N, 7.06. Found: C, 57.58; H, 4.06; N, 7.03. yield.

G DOI: 10.1021/om5009378
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Organometallics Article
1
H NMR (400 MHz, CD2Cl2, δ (ppm)) 8.52 (s, 1H), 8.20 (s, 1H), (E)-4-(4-ethynylstyryl)-N,N-diphenylaniline (8.0 mg, 0.0216 mmol)
8.11 (d, J = 7.8 Hz, 1H), 8.00 (s, 1H), 7.95 (d, J = 7.8 Hz, 1H), 7.29− was added, and the solution was heated at 40 °C for 2 h. After cooling
7.01 (m, 45H), 3.98 (s, 3H), 2.71 (m, 8H), 1.55−1.39 (m, 16H), to room temperature, the reaction mixture was filtered, and the
1.58−1.55 (m, 10H). inorganic salts were washed with CH2Cl2 (1 mL). Et2O was added to
MS (MALDI-TOF, 2-[(2E)-3-(4-tert-butylphenyl)-2 methylprop-2- the CH2Cl2 extract to precipitate the vinylidene salt as a violet powder,
enylidene]malonitrile as the matrix) calcd for C93H87N3O2P4RuS3 m/z which was collected by filtration and then under nitrogen was
1599.40, found 1600.7. Anal. Calcd: C, 69.82; H, 5.48; N, 2.63. Found: redissolved in CH2Cl2 (1 mL). TEA (50 μL) was added and stirring
C, 69.99; H, 5.39; N, 2.60. was maintained for 2 h, the solvent was removed under reduced
Complex F was prepared starting from 45 mg of the potassium salt pressure, and the residue was taken up in CH2Cl2 and purified by
derivative of 5. column chromatography (basic alumina). Elution with CH2Cl2 gave a
The intermediate was obtained in 95% yield in more basic condition yellow band that was collected and dried in vacuo. The yellow product
than previous described for 5. was obtained in 85% yield
Starting from 4 (50 mg, 0.074 mmol), K2CO3 (20.4 mg, 0.148 1
H NMR (400 MHz, CD2Cl2): 7.77 (d, JH‑H = 8.6 Hz, 2H), 7.40−
mmol) in THF/MeOH (1:1, 6 mL) at 30 °C for 1 h. The solvent was 7.19 (m, 20H), 7.13 (d, JH‑H = 8.6 Hz, 2H), 7.11−6.98 (m, 36H), 2.68
removed under reduced pressure, and the residue was purified by flash (m, 8H). Elemental Analysis: Calcd for C80H68ClNP4Ru: C, 73.70; H,
chromathography on silica gel (hexane/ethyl acetate 8:2). The acid 5.26; N, 1.07. Found: C, 74.05; H, 5.29; N, 1.09.
was obtained dissolving the residue in CH2Cl2 and adding the Synthesis of Complex C. 11 (25.0 mg, 0.019 mmol), 4-ethynyl-
stoichiometric amount of trifluoroacetic acid. 1H NMR (400 MHz, benzaldehyde (2.6 mg, 0.02 mmol), and NaPF6 (1.0 mg, 0.076 mmol)
CD2Cl2, δ (ppm)) 8.51 (s, 1H), 8.20 (s, 1H), 8.08 (d, J = 7.8 Hz, 1H), were dissolved in CH2Cl2 (2 mL), and the solution was stirred for 1 h.
7.96(s, 1H), 7.95 (d, J = 7.8 Hz, 1H), 7.28−7.03 (m, 45H), 2.72 (m, TEA (50 μL) was added, and stirring was maintained for 24 h at room
8H), 1.55−1.39 (m, 16H), 1.58−1.55 (m, 10H). temperature with exclusion of light. The reaction mixture was filtered,
MS (MALDI-TOF, 2-[(2E)-3-(4-tert-butylphenyl)-2 methylprop-2- the inorganic salts were washed with CH2Cl2 (1 mL), and the solvent
enylidene]malonitrile as the matrix) calcd for C92H84KN3O2P4RuS3 was removed under reduced pressure.
m/z 1623.34, found 1624.0. Anal. Calcd: C, 68.04; H, 5.21; N, 2.59. The residue was taken up in CH 2 Cl 2 and purified by
Found: C, 68.02; H, 5.21; N, 2.60. chromatography on neutral alumina, elution with hexane/CH2Cl2
Synthesis of Complexes C, D, and E (see Schemes 2 and 3 in 9:1, and then 1:1 gave an orange band that was collected and
Results and Discussion). Synthesis of (E)-4-(4-Bromostyryl)-N,N- evaporated under reduced pressure. The orange product was obtained
diphenylaniline (8). To a solution of diethyl 4-bromobenzyl-
in 90% yield.
phosphonate (364.0 mg, 1.2 mmol, 1.1 equiv) and 4-(diphenyl- 1
H NMR (400 MHz, CD2Cl2): 9.95 (s, 1H), 7.74 (d, JH‑H = 8.6 Hz,
amino)benzaldehyde (295.0 mg, 1.08 mmol, 1 equiv) in THF (9 mL),
2H), 7.40−7.19 (m, 19H), 7.13 (d, JH‑H = 8.6 Hz, 2H), 7.11−6.98 (m,
under nitrogen, and cooled to 0 °C, was added, in small portions,
37H), 6.93 (d, JH‑H = 8.9 Hz, 2H), 6.78 (d, JH‑H = 8.9 Hz, 2H), 2.68
potassium tert-butoxide (316.0 mg, 2.8 mmol, 2.6 equiv). The cool
(m, 8H). Elemental Analysis: Calcd for C89H73NOP4Ru: C, 76.49; H,
bath was then removed and the mixture stirred for 18 h at room
5.27; N, 1.00. Found: C, 76.89; H, 5.25; N,0.98.
temperature. After hydrolysis with water, the mixture was stirred for a
Synthesis of Complexes D and E. To a solution of Complex C
further 30 min. The reaction mixture was diluted with AcOEt and
(10.0 mg, 0.007 mmol) and methylcyanoacetate (2.52 μL, 0.02 mmol)
washed with water: the organic layer was dried over Na2SO4 and
or cyanoacetic acid (13.0 mg, 0.02 mmol) in acetonitrile/CH2Cl2 1:1
concentrated. The crude product obtained was purified by flash
(4 mL) was added piperidine (10 μL, 0.431 mmol, 7.0 equiv). After
chromatography, using hexane/dichloromethane 1:1 as eluant, to give
stirring at room temperature overnight, the solvent was removed
the product as a pale yellow solid (378 mg; yield 85%). Character-
under reduced pressure. The residue was taken up in CH2Cl2 and
ization was performed by 1H and 13C NMR, and it is consistent with
diethyl ether was added, and the precipitate was filtered, and was
published data.
Synthesis of (E)-N,N-Diphenyl-4-(4-((trimethylsilyl)ethynyl)styryl)- washed with diethyl ether (1 mL). The filtrate was evaporated under
aniline (9). To a solution of (E)-4-(4-bromostyryl)-N,N-diphenyl- reduced pressure, and the product was recrystallized.
aniline (8) (280.0 mg, 0.47 mmol, 1 equiv) and ethynyltrimethylsilane Complex D: Orange/red product was obtained by slow diffusion of
(69.2 mg, 0.7 mmol, 1.5 equiv) in a degassed tetrahydrofuran (7.8 pentane into CH2Cl2 solution (8.0 mg, 80%). 1H NMR (400 MHz,
mL), under a flow of nitrogen, were added [PdCl2(PPh3)2] (13.2 mg, CD2Cl2): 8.03 (s, 1H), 7.72 (d, JH‑H = 8.6 Hz, 2H), 7.55−7.44 (m,
4 mol %), CuI (5.4 mg, 6 mol %), and triethylamine (2 mL). The 19H), 7.30 (d, JH‑H = 8.6 Hz, 2H), 7.32−7.13 (m, 39H), 6.82−6.77
reaction mixture was left under stirring at 70 °C overnight. The solvent (m, 2H), 3.95 (s, 3H), 2.70 (m, 8H). Elemental Analysis: Calcd for
was removed under reduced pressure, and the residue was purified by C93H76N2O2P4Ru: C, 75.55; H, 5.18; N, 1.89. Found: C, 75.59; H,
flash chromatography, using hexane/dichloromethane 9:1 as eluant, to 5.16; N, 1.89 MS(MALDI) calcd. m/z: 1478.34 found: 1478.0
give 9 as a yellow solid (157 mg; yield 75%). Characterization was (product), 897.2 (Ru(dppe)2).
performed by 1H and 13C NMR, and it is consistent with published Complex E: The acid was obtained dissolving the residue in CH2Cl2
data. and adding the stoichiometric amount of trifluoroacetic acid. Orange
Synthesis of (E)-4-(4-Ethynylstyryl)-N,N-diphenylaniline (10). To a crystals of product were obtained by slow diffusion of pentane into
solution of (E)-N,N-diphenyl-4-(4-((trimethylsilyl)ethynyl)styryl)- CH2Cl2 solution (9.0 mg, 91%). 1H NMR (400 MHz, CD2Cl2): 8.05
aniline (9) (71.3 mg, 0.16 mmol, 1 equiv), in methanol (5.3 mL), (s, 1H), 7.78 (d, JH‑H = 8.6 Hz, 2H), 7.60−7.44 (m, 19H), 7.35 (d, JH‑H
under a flow of nitrogen, was added K2CO3 anhydrous (88.4 mg, 0.64 = 8.6 Hz, 2H), 7.32−7.13 (m, 39H), 6.82−6.77 (m, 2H), 2.70 (m,
mmol, 4 equiv). The reaction mixture was left under stirring at room 8H). Elemental Analysis: Calcd for C92H74N2O2P4Ru: C, 75.45; H,
temperature overnight. The solvent was removed under reduced 5.09 N, 1.91. Found: C, 75.65; H, 5.07; N, 1.89 MS(MALDI) m/z:
pressure, and the residue was diluted with CH2Cl2 and washed with 1469.6 (COO−Li+), 1270.3 (Ru(CC-4-(E)-ethynylstyryl-N,N-
water: the organic layer was dried over Na2SO4 and concentrated. The diphenylaniline) (dppe)2), 897.2 (Ru(dppe)2).
crude product obtained was purified by flash chromatography, using EFISH Measurements. All EFISH measurements40−42 were
hexane/dichloromethane 8:2 as eluant, to give 5 as a yellow solid (54.0 carried out at the Dipartimento di Chimica of the Università degli
mg; yield 90%). MS(FAB+): m/z 371. Characterization was performed Studi di Milano, in CH2Cl2 solutions at a concentration of 1 × 10−3 M,
by 1H and 13C NMR, and it is consistent with published data. working with a nonresonant incident wavelength of 1.907 μm,
Synthesis of trans-[Ru(CC-4-(E)-Ethynylstyryl-N,N-diphenyl- obtained by Raman-shifting the fundamental 1.064 μm wavelength
aniline)Cl(dppe)2][PF6] (11). trans-[Ru(dppe)2Cl2] (20.0 mg, 0.019 produced by a Q-switched, mode-locked Nd3+:YAG laser manufac-
mmol) and NaPF6 (3.6 mg, 0.0216 mmol) were dissolved in CH2Cl2 tured by Atalaser. The apparatus for the EFISH measurements is a
(1 mL), and the solution was stirred for 12 h at room temperature prototype made by SOPRA (France). The μβEFISH values reported are
with exclusion of light. the mean values of 16 successive measurements performed on the

H DOI: 10.1021/om5009378
Organometallics XXXX, XXX, XXX−XXX
Organometallics Article

same sample. The sign of μβ is determined by comparison with the

reference solvent (CH2Cl2).
Computational Details. All the calculations have been performed
■ ACKNOWLEDGMENTS
We deeply thank Mattia Fontana for some experimental help.
by the Gaussian 09 program package.78 Geometry optimizations of the This work was supported by MIUR and by eni (Contract
various ruthenium complexes were performed in vacuo, using the number 3500005452).

■
B3LYP exchange-correlation functional79 and using a LANL2DZ basis
set80 for all atoms along with the corresponding pseudopotentials for
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I DOI: 10.1021/om5009378
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