Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and Gases

Article abstract of DOI:10.1002/chem.201903303

A series of new ruthenium(II) vinyl complexes has been prepared incorporating perylenemonoimide (PMI) units. This fluorogenic moiety was functionalised with terminal alkyne or pyridyl groups, allowing attachment to the metal either as a vinyl ligand or th

Full text of DOI:10.1002/chem.201903303

DOI: 10.1002/chem.201903303
Full Paper
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Organometallic Chemistry |Hot Paper|
Synthesis and Application of Ruthenium(II) Alkenyl Complexes
with Perylene Fluorophores for the Detection of Toxic Vapours
and Gases
Josꢀ Garcꢁa-Calvo,[a] Jonathan A. Robson,[b] Tomꢂs Torroba,*[a] and James D. E. T. Wilton-Ely*[b]
Abstract: A series of new ruthenium(II) vinyl complexes has
been prepared incorporating perylenemonoimide (PMI)
units. This fluorogenic moiety was functionalised with termi-
nal alkyne or pyridyl groups, allowing attachment to the
metal either as a vinyl ligand or through the pyridyl nitro-
gen. The inherent low solubility of the perylene compounds
was improved through the design of poly-PEGylated (PEG=
polyethylene glycol) units bearing a terminal alkyne or a pyr-
idyl group. By absorbing the compounds on silica, vapours
and gases could be detected in the solid state. The reaction
of the complexes [Ru(CH=CH-PerIm)Cl(CO)(py-3PEG)(PPh3)2]
and [Ru(CH=CH-3PEG)Cl(CO)(py-PerIm)(PPh3)2] with carbon
monoxide, isonitrile or cyanide was found to result in modu-
lation of the fluorescence behaviour. The complexes were
observed to display solvatochromic effects and the interac-
tion of the complexes with a wide range of other species
was also studied. The study suggests that such complexes
have potential for the detection of gases or vapours that are
toxic to humans.
tridentate[16] donors can be coordinated to these vinyl com-
pounds. This provides ample demonstration of the reactivity at
the metal centre, however, the installation of the vinyl ligand
through facile reaction with terminal alkynes (also internal al-
kynes under more forcing conditions) allows the incorporation
of further functionality that can be influenced by the metal
centre.[17] Our recent work has demonstrated the potential of
this approach through the selective detection of very low con-
centrations of carbon monoxide both in air[12a,b] and in
cells,[12c,d] following work by others in the area.[12e–t] Among
other features, this contribution provides an illustration of the
versatility of such ruthenium vinyl complexes to install a fluo-
rophore either through coordination to the metal centre or as
the substituent of the vinyl itself.
Introduction
The growth in interest in vinyl complexes of the heavier con-
geners of group 8 started around 30 years ago[1–9] and, since
then, these versatile complexes have attracted much attention.
Although other approaches are known, the most widely used
route to ruthenium vinyl complexes, such as the 5-coordinate
compounds [Ru(CR=CHR’)Cl(CO)(PR3)2] (R=Ph, iPr), is through
the hydrometallation of alkynes by the compounds [RuHCl(-
CO)(PPh3)3][1a] and [RuHCl(CO)(PiPr3)2].[3a] Harris and Hill report-
ed a modification of this approach to yield triphenylphosphine
derivatives, which avoided contamination with tris(phosphine)
side products by using [RuHCl(CO)(BSD)(PPh3)2] as the precur-
sor.[10a] The labile 2,1,3-benzoselenadiazole (BSD) ligand permit-
ted insertion of alkynes into the RuÀH bond to yield the coor-
dinatively-saturated products [Ru(CR=CHR’)Cl(CO)(BSD)(PPh3)2]
(R, R’=H or alkyl/aryl substituents).[10a] Our work has focused
on the analogous 2,1,3-benzothiadiazole (BTD) complexes, in-
cluding osmium examples,[10b] which use the cheaper BTD het-
erocycle. Through the lability of the chloride and phosphine li-
gands (and BTD/BSD, if present), mono-,[11,12] bi-[13,14,15] and
Perylenemonoimide (PMI) compounds have been demon-
strated to be effective fluorescent signalling units for use in
fluorogenic sensors.[18] They possess many advantages with re-
spect to other more classical and widely-used fluorescent mol-
ecules, such as BODIPY (boron dipyrromethene) derivatives.
For example, they display excitation/emission wavelengths in
the visible and near-IR regions of the spectrum, which offer
substantial advantages in terms of biological imaging. As well
as excellent thermal and photo-stability, PMI compounds are
tolerant towards a wide range of different reagents and are
easily functionalised, for example by bromination followed by
Suzuki coupling.[19] All the above characteristics are exploited
here to allow the incorporation of PMI units into divalent
ruthenium vinyl complexes for application in the detection of
a range of analytes. The use of silica supports in this work pro-
vides an illustration of the application of these inorganic mate-
rials as an inexpensive and efficient method for enhancing the
application of colorimetric or fluorogenic chemosensors.[12,19]
[a] Dr. J. Garcꢀa-Calvo, Prof. Dr. T. Torroba
Department of Chemistry, Faculty of Science
University of Burgos, 09001 Burgos, (Spain)
E-mail: ttorroba@ubu.es
[b] Dr. J. A. Robson, Prof. Dr. J. D. E. T. Wilton-Ely
Department of Chemistry, Imperial College London
Molecular Sciences Research Hub, White City Campus
London, W12 0BZ (UK)
E-mail: j.wilton-ely@imperial.ac.uk
Supporting information and the ORCID identification number(s) for the
author(s) of this article can be found under:
https://doi.org/10.1002/chem.201903303.
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Scheme 1. Two approaches to functionalising ruthenium vinyl complexes with fluorogenic units. FL=fluorophore, SOL=solubilizing unit.
Results and Discussion
Two different approaches were used to incorporate
fluorescent units into ruthenium vinyl complexes.[12]
The two designs are shown in Scheme 1 and involve
the fluorophore as either the vinyl substituent or the
ligand directly attached to the metal centre.
The benefits of mechanism A include the fact that
the fluorophore is retained within the metal complex,
ensuring that the metal complex is located where
fluorescence is observed. The fluorogenic response
originates from the electronic changes caused by dis-
placement of the ligand trans to the vinyl group by
the analyte (L). This also leads to a modulation of the
colour observed in many cases. However, mechanism
B can often result in a greater fluorescence revival as
Scheme 2. Synthesis of new perylene monoimide derivatives.
the fluorophore is completely detached from the metal centre,
allowing the quenching (heavy atom effect[20]) to be fully re-
moved, resulting in a turn-ON fluorescence response.[21] A pos-
sible disadvantage of mechanism B is that premature displace-
ment of the fluorophore is more likely and that, once displace-
ment occurs, the fluorophore and the metal complex may not
remain co-localised. However, this design does allow the facile
addition of other functional units (e.g., to enhance solubility or
cellular targeting) to the vinyl ligand through use of a func-
tionalised terminal alkyne.
chromatography (silica gel) and were obtained as red solids in
good yields (further details in Supporting Information).
Perylenemonoimide compounds often suffer from poor solu-
bility and it was considered likely that this characteristic would
also be imparted to their metal complexes. It was therefore de-
cided to devise a solubilizing unit that could be used with
both designs shown in Scheme 1. This led to the synthesis of a
structure with three polyethylene glycol chains and this was
used to generate two new pyridyl (py-PEG3) and alkynyl (HCꢀ
C-PEG3) derivatives (Scheme 3).
These solubilizing units, py-PEG3 and HCꢀC-PEG3, were
fully characterised by 1H, 13C{1H} NMR and infrared spectros-
copies and mass spectrometry. Both py-PEG3 and HCꢀC-PEG3,
were obtained as pale yellow oils after purification by column
chromatography in DCM/MeOH mixtures. Characteristic signals
were observed, such as the 5.26 ppm singlet attributed to the
Synthesis of fluorophores and solubilizing units
To explore both sensing mechanisms shown in Scheme 1, two
new PMI derivatives, py-perIm and HCꢀC-perIm, were prepared
with pyridyl and ethynyl functionality. This was achieved start-
ing from the 9-bromo derivative, as shown in Scheme 2.
The synthesised compounds, py-perIm and HCꢀC-perIm,
1
terminal alkyne in the H NMR spectrum (see Supporting Infor-
mation).
With the perylenemonoimide fluorophores and the comple-
mentary PEGylated solubilizing units prepared, the focus
moved to the synthesis of the ruthenium vinyl complexes.
1
were fully characterised using H and 13C{1H} NMR and infrared
spectroscopies and mass spectrometry. Both compounds pos-
sess an imide group with a bulky aliphatic group (1-adaman-
tyl-ethylamine) to increase solubility and were synthesised
using palladium-catalysed CÀC coupling approaches. A Suzuki
reaction was used to prepare py-perIm while HCꢀC-perIm was
obtained as the product of a Sonogashira coupling after a de-
protection step. Both compounds were purified using column
Ruthenium vinyl complexes
Two approaches were employed to synthesise the new ruthe-
nium vinyl complexes reported in this contribution. The most
straightforward method utilises the 5-coordinate triphenyl-
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(phosphine) compound, [RuHCl(CO)(PPh3)3]. The second ap-
proach takes this hydride compound and converts it to the
cationic bis(acetonitrile) adduct, [RuH(CO)(NCMe)2(PPh3)2]+,[2e,22]
which reacts with alkynes to form [Ru(CH=CHR)(CO)(NC-
Me)2(PPh3)2]+[2e] before halide addition yields the neutral com-
pound [Ru(CH=CHR)Cl(CO)(NCMe)(PPh3)2], in which the labile
acetonitrile ligand can be readily substituted.
Reaction of [RuHCl(CO)(PPh3)3] with HCꢀC-perIm in dichloro-
methane solution generated the 5-coordinate [Ru(CH=CH-
perIm)Cl(CO)(PPh3)2] in situ. Addition of py-PEG3 led to forma-
tion of the dark blue complex [Ru(CH=CH-perIm)Cl(CO)(py-
PEG3)(PPh3)2] (3PEG-Ru-CH=CH-perIm) in 84% yield (Scheme 4).
A singlet in the 31P{1H} NMR spectrum at 26.2 ppm indicated
the presence of mutually trans phosphine ligands. In the
1H NMR spectrum, the retention of the vinyl ligand was con-
firmed by characteristic doublets (JHH =16.3 Hz) for the Ha and
Hb protons at 9.59 and 6.96 ppm, respectively. Typical resonan-
ces for the perylene unit were observed between 8.02–
8.39 ppm (aromatic) and 1.63–1.98 ppm (adamantyl), with a di-
agnostic resonance at 5.09 ppm for the CH(Me)Ad proton. Pyr-
idyl resonances were observed at 7.66 and 8.74 ppm, confirm-
ing the presence of the water-solubilizing unit. The carbonyl
groups were clearly visible in the 13C{1H} NMR spectrum at
Scheme 3. Synthesis of PEGylated units suitable for use in aqueous and
polar solvents.
phosphine compounds first reported by Santos and co-work-
ers,[1a] [Ru(CH=CHR)Cl(CO)(PPh3)2], which are formed by the hy-
drometallation of alkynes by the commercially-available tris-
Scheme 4. Synthesis of ruthenium vinyl complexes.
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203.6 ppm (RuCO), and between 166.0–164.6 ppm (amide and
ester groups). The carbon monoxide ligand bonded to the
metal gave rise to an absorption at 1926 cmÀ1 while the ester
and amide carbonyls contributed to a broader resonance at
1734 cmÀ1. The overall composition was confirmed by mass
spectrometry data and good agreement between calculated
and measured elemental analysis values.
ensure that there is little doubt as to the composition of these
complexes.
Photophysical characterisation
The absorbance and fluorescence properties of the synthesised
compounds were investigated in solution (Table 1). All of the
PMI derivatives displayed high molar extinction coefficients
and around three times greater quenching of the fluorescence
for the complexes compared to the ligands HCꢀC-perIm and
py-perIm. It was also found that the fluorescence lifetime decay
values increased by 0.12 ns in the complexes over those mea-
sured for the ligands.
The bis(acetonitrile) cation, [RuH(CO)(NCMe)2(PPh3)2]BF4 re-
acted with HCꢀC-perIm in dichloromethane solution to initially
yield [Ru(CH=CH-PEG3)(CO)(NCMe)2(PPh3)2]BF4, before addition
of [NEt4]Cl gave the neutral [Ru(CH=CH-PEG3)Cl(CO)(NC-
Me)(PPh3)2] (Scheme 4). The labile acetonitrile ligand was readi-
ly displaced by py-perIm to yield the red complex, [Ru(CH=CH-
PEG3)Cl(CO)(py-perIm)(PPh3)2] (3PEG-Ru-py-perIm) in 65% over-
all yield. The purity of the product was indicated by the pres-
ence of only one singlet at 26.7 ppm in the 31P{1H} NMR spec-
Table 1. Photophysical parameters of the different PMI derivatives syn-
thesised.
trum, while the vinyl ligand gave rise to two doublets (JHH
=
16.8 Hz) at 9.35 and 6.00 ppm for the Ha and Hb protons, with
the lower field resonance displaying broadening due to cou-
pling with the mutually trans phosphines. The presence of the
coordinated py-perIm unit was indicated by pyridyl resonances
at 7.85 and 8.76 ppm as well as a diagnostic quartet at
5.10 ppm for the CH(Me)Ad proton. Good agreement between
calculated and determined elemental analysis values confirmed
the overall composition along with MALDI mass spectrometry
data (Supporting Information).
Compound
loge (lmax
)
F [%] (Æ2%)
(CH2Cl2)
90
91
38
t [ns]
c
(CHCl3)
(CH2Cl2)
4.62
4.45
4.74
4.57
HCꢀC-perIm
4.7 (500 nm)
4.5 (500 nm)
4.7 (575 nm)
4.7 (500 nm)
1.085
1.116
1.078
1.098
py-perIm
3PEG-Ru-CH=CH-perIm
3PEG-Ru-py-perIm
29
The absorption and fluorescence studies also showed that
3PEG-Ru-CH=CH-perIm displayed a remarkable bathochromic
shift with polarity. It was also noted that the absorption bands
were broader than in the free perylenemonoimides, partly
overlapping with the emission bands. The absorption and fluo-
rescence of 3PEG-Ru-py-perIm was found to depend on the
solvent in the same way as its perylenemonoimide precursor
py-perIm. Complexation to a metal served to increase its solu-
bility, rendering it slightly soluble in organic:water mixtures,
however, the fluorescence was found to be quenched under
these conditions.
There is considerable interest in ratiometric probes in which
two fluorophores are combined within the same molecule.[23]
This allows detection of an analyte through two different emis-
sion responses. Previously, we have used the 5-(3-thienyl)-
2,1,3-benzothiadiazole (TBTD) fluorophore (lexc =355 nm, lem
=
500 nm) to detect carbon monoxide in cells and in a mouse
model of inflammation.[12c,d] This fluorophore could also be ex-
cited under two-photon conditions[12c] at 715 nm to allow de-
tection of endogenous CO at extremely low probe concentra-
tions. It was therefore decided to explore the installation of
both the perylenemonoimide (PMI) and TBTD fluorophores
within the same complex. Treatment of [RuHCl(CO)(PPh3)3]
with HCꢀC-perIm in dichloromethane led to in situ generation
of [Ru(CH=CH-perIm)Cl(CO)(PPh3)n] (n=2 or 3) before addition
of the TBTD ligand, which provided the dark blue compound
[Ru(CH=CH-perIm)Cl(CO)(TBTD)(PPh3)2] (TBTD-Ru-CH=CH-perIm)
In general, it was found that there was little difference in the
absorption and fluorescence behaviour of 3PEG-Ru-CH=CH-
perIm and TBTD-Ru-CH=CH-perIm. The only exception to this
was the observation of an absorption in the region 300–
400 nm, attributed to the absorption of the TBTD fluorophore
(Figure S4.2 in Supporting Information).
1
in 71% overall yield. The H NMR spectrum was again the most
After this initial evaluation of the photophysical parameters,
a solvatochromic (Figures S2.16, S2.21, S2.26 and S2.31 in the
Supporting Information) and solubility study led to acetone
being chosen as the optimal solvent for testing the response
to other analytes (Supporting Information).
diagnostic characterisation method, displaying clear resonan-
ces for the CH=CH-perIm unit at 9.41 (Ha), 6.94 (Hb) and 5.08
(CH(Me)adamantyl) ppm as well as features between 1.5–
2.0 ppm for the adamantyl unit. In the same spectrum, the
TBTD ligand gave rise to resonances at 7.63, 7.74 and
7.86 ppm. The overall composition was supported by MALDI
data and satisfactory elemental analysis values for the dichloro-
methane solvate. Substantial effort was invested in attempts
to grow single crystals of all ruthenium complexes suitable for
a structural determination, but without success. The difficulty
in obtaining structural data on PMI derivatives has been re-
marked upon previously.[18] However, the presence of charac-
teristic features in the NMR and IR spectra and the many estab-
lished examples of ruthenium vinyl complexes of this type
The coordinated PMI complexes were screened against a
series of 16 different cations (Section S4.4 in Supporting Infor-
mation). For 3PEG-Ru-CH=CH-perIm, little change was ob-
served apart from in the presence of Cu2+ when irradiated
with UV light (Figure S4.12 in ESI). The effect of different pH
conditions was also investigated with this PMI compound,
which revealed little change until a highly basic aqueous solu-
tion (pH 12.3) was reached, likely due to chemical modification
of the complex itself (Figure S4.13. in ESI). For 3PEG-Ru-py-
perIm there was no significant change in the fluorescence
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properties except with Au3+ cations (Figure S4.14), which
could be a result of the acidity of the HAuCl4 used.
Eleven different anions were screened for interactions with
the perylene moiety in the complexes. In almost all cases, little
significant change was observed. An exception was a colour
change to pale blue and the observation of a red emission for
3PEG-Ru-CH=CH-perIm with cyanide ions (Figure S4.15). This
was attributed to the p-acid cyanide forming a complex with
the ruthenium compound in a similar way to that found with
carbon monoxide.[12] This result led to an investigation of the
sensing potential of the complexes with a series of p-acid ana-
lytes. It was of particular interest to explore the detection of
toxic substances found as gases or vapours as the risk of expo-
sure is particularly great. The detection of carbon monoxide
(CO), cyanide (CNÀ) and a representative isonitrile (tBuNC) was
studied. Accordingly, it was found that 5 mm solutions of the
probes 3PEG-Ru-CH=CH-perIm and 3PEG-Ru-py-perIm dis-
played spectroscopic changes in presence of these analytes
(Figure 1 and Figure 2).
Figure 3. Absorbance (top) and fluorescence (bottom) spectra of 3PEG-Ru-
CH=CH-perIm (5 mm) with [NBu4]CN (50 mm), CO (bubbled for 2 min) and
tBuNC (50 mm) in acetone solution.
3PEG-Ru-CH=CH-perIm while the corresponding value for
3PEG-Ru-py-perIm was 0.41 mm (10.7 mgLÀ1). For the isonitrile
tBuNC, the LOD was measured to be 0.29 mm (24.1 mgLÀ1) for
3PEG-Ru-CH=CH-perIm and 0.12 mm (10 mgLÀ1) for 3PEG-Ru-
py-perIm. Across all experiments, the results showed a very
high sensitivity for both cyanide and isocyanide as analytes
(Section S4.5 in Supporting Information).
Figure 1. Colour (left) and fluorescence (right) responses of 3PEG-Ru-CH=
CH-perIm (5 mm) to NBu4CN (50 mm), CO (bubbled for 2 min) and tBuNC
(50 mm) in acetone solution. Reference=acetone solution of the original
complex.
Silica immobilisation of the complexes
Detection of analytes, such as cyanide, in solution is important
due to its common occurrence as an environmental pollutant
in ground water.[25] Such applications, where measurement is
often undertaken by non-specialists, are served best by simple,
low-cost and easily-used systems, such as colorimetric meth-
ods.[23] The use of colour strips has been investigated in our
earlier work on carbon monoxide detection and this approach
proved successful,[12a,b] whether analysis was performed by the
naked eye or by an optoelectronic device.[26] With this in mind,
the compounds 3PEG-Ru-CH=CH-perIm and 3PEG-Ru-py-perIm
were immobilised on a silica support backed by an aluminium
sheet (TLC, silica gel 60, Merck). The absorption was performed
by dissolving the compound (2 mg) in toluene (25 mL) and
then submerging the TLC plates (5ꢄ5 cm) in the solution over-
night at 608C. The solution became colourless and successful
immobilisation of the compound on the silica was confirmed
by the bright colours observed for the plates (Figure 4).
Figure 2. Colour (left) and fluorescence (right) responses of 3PEG-Ru-py-
perIm (5 mm) to NBu4CN (50 mm), CO (bubbled for 2 minutes) and tBuNC
(50 mm) in acetone solution. Reference=acetone solution of the original
complex.
In contrast, acetone solutions of 3PEG-Ru-py-perIm produces
an increase in fluorescence for all three analytes ([NBu4]CN, CO
and tBuNC), with little differentiation between them. The sig-
nificant colour and fluorescence changes displayed by 3PEG-
Ru-CH=CH-perIm depending on the analyte are reflected in the
quantitative data shown in Figure 3.
Using the absorbance and fluorescence data, several titra-
tions were carried out, which allowed calculations to be per-
formed to determine the limit of detection (LOD) in solution
for cyanide and tBuNC.[24] A limit of detection of 0.29 mm
(7.55 mgLÀ1) was recorded for cyanide with probe
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Figure 4. Image of the TLC plates with absorbed 3PEG-Ru-CH=CH-
perIm (left) and 3PEG-Ru-py-perIm (right).
In a similar way to the behaviour observed in solution, the
immobilised complexes gave rise to fluorescence changes after
short periods in an atmosphere with CO gas or when isonitrile
or BrCN vapours were present. Using the apparatus shown in
Figure 5, these gases/vapours were found to lead to distinct
changes in colour/fluorescence for each analyte without the
need for any solvent.
Figure 6. Qualitative response of the TLC plates modified with 3PEG-Ru-
CH=CH-perIm (top) and 3PEG-Ru-py-perIm (bottom) in the presence of differ-
ent vapours/gases with measurement after 6 hours.
The experiments were performed for both the modified TLC
plates based on 3PEG-Ru-CH=CH-perIm and 3PEG-Ru-py-perIm
(See Section S4.5 in Supporting Information). In order to mea-
sure the colour changes on reaction with the analyte, the im-
mobilised compounds were exposed to a constant stream of
CO to saturate the chamber and the changes were then stud-
ied over time. In a similar process, the TLC plates were placed
in sealed 15 mL vials with 20 mL of tBuNC or 5 mg of BrCN at
room temperature. The response observed depended on the
vapour pressure of the compound and the interaction with the
supported probe, as can be seen in Figure 6.
At constant vapour pressure, the changes of colour and fluo-
rescence of the immobilised compounds were found to
depend on time. When studying the response to tBuNC, it was
enough to wait for only 30 minutes to observe a significant in-
crease in fluorescence, with both probes reaching the satura-
tion point after 2–3 hours (Figure 7).
Figure 5. Representation of the method employed to expose the modified
TLCs to different vapours or gas.
Figure 7. Colour and fluorescence responses of immobilised 3PEG-Ru-CH=CH-perIm (left) and 3PEG-Ru-py-perIm (right) to tBuNC vapour over time, based on
the emission at 620 nm (lexc =515 nm).
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Figure 8. Colour and fluorescence responses of immobilised 3PEG-Ru-CH=CH-perIm (left) and 3PEG-Ru-py-perIm (right) to BrCN vapour over time, based on
the emission at 620 nm (lexc =515 nm).
Figure 9. Colour and fluorescence responses of immobilised 3PEG-Ru-CH=CH-perIm (left) and 3PEG-Ru-py-perIm (right) to a stream of CO over time, based on
the emission at 625 nm (lexc =515 nm).
Conclusions
In contrast, the response was completely different when
evaluating the reaction with BrCN, which produced only a
small increase in fluorescence for the supported probe 3PEG-
The first fluorescent ruthenium(II) vinyl complexes based on
the perylenemonoimide (PMI) fluorophore have been synthes-
ised and characterised and their photophysical properties in-
vestigated. While one ruthenium example based on a peryle-
nebisimide design has been reported (as a photosensitizer for
photodynamic therapy),[19f] these solvatochromic compounds
represent the first examples of ruthenium with PMI-based li-
gands. Using the inherent versatility of these compounds, both
the vinyl substituent and the coordination site at the metal
centre were used to introduce the PMI fluorophore. To increase
the solubility and stability of the complexes in solution, two
new water-solubilizing moieties were designed and introduced
through either the vinyl ligand or a pyridyl unit. The two de-
signs allowed sensing mechanisms based on a) modulation of
the fluorescence of the retained fluorophore through ligand
Ru-CH=CH-perIm, reaching
a maximum after 2–3 hours
(Figure 8, left). However, in contact with BrCN vapour, the fluo-
rescence of immobilised 3PEG-Ru-py-perIm was almost totally
quenched after one hour (Figure 8, right).
The behaviour of the immobilised probes with CO was
found to be very similar to those obtained in solution, with
the fluorescence increasing rapidly in the presence of a con-
stant stream of CO (saturated atmosphere). Saturation occurs
in less than 30 minutes and the response is similar to that ob-
served with tBuNC vapour, although with a smaller increase in
fluorescence for both of the immobilised systems (Figure 9
and Figures 1 and 2).
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substitution (3PEG-Ru-CH=CH-perIm) and b) displacement of
the fluorophore to be investigated (3PEG-Ru-py-perIm). In ace-
tone solution, the compounds displayed a particular affinity for
the p-acid species investigated. This led to preliminary studies
in which the probes proved effective for the detection of sev-
eral toxic analytes (isonitrile, cyanide and carbon monoxide),
not only in solution but supported on silica. In particular, the
probes showed very low limits of detection (LOD) for cyanide
(0.29 mm) and tertiarybutylisonitrile (0.12 mm) in solution and
sensitive detection of these analytes as vapours in less than an
hour when the probes were immobilized on silica.
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Acknowledgements
We gratefully acknowledge financial support from the Minister-
io de Economꢁa y Competitividad, Spain (Project CTQ2015-
71353-R) and Junta de Castilla y Leꢅn, Consejerꢁa de Educaciꢅn
y Cultura y Fondo Social Europeo (Project BU263P18). J.G.C.
thanks the Ministerio de Economꢁa y Competitividad for his
predoctoral FPU fellowship and J.A.R. is grateful to the Engi-
neering and Physical Sciences Research Council (UK) for a DTP
Studentship.
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Keywords: coordination chemistry · perylene · ruthenium ·
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Manuscript received: July 19, 2019
Accepted manuscript online: August 27, 2019
Version of record online: && &&, 0000
Chem. Eur. J. 2019, 25, 1 – 10
www.chemeurj.org
9
ꢃ 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Full Paper
FULL PAPER
Sensors: The first reported examples of
ruthenium(II) vinyl complexes bearing
perylenemonoimide units are able to
detect carbon monoxide, isonitriles or
cyanide through fluorescence changes
(see figure).
&
Organometallic Chemistry
J. Garcꢀa-Calvo, J. A. Robson, T. Torroba,*
J. D. E. T. Wilton-Ely*
&& – &&
Synthesis and Application of
Ruthenium(II) Alkenyl Complexes with
Perylene Fluorophores for the
Detection of Toxic Vapours and Gases
&
&
Chem. Eur. J. 2019, 25, 1 – 10
www.chemeurj.org
10
ꢃ 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!