A ruthenium(III) complex derived from: N, N ′-bis(salicylidene)ethylenediamine as a chemosensor for the selective recognition of acetate and its interaction with cells for bio-imaging: Experimental and theoretical studies

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New Journal of Chemistry

ARTICLE

Ruthenium(III)

complex

derived

from

N,N´-

bis(salicylidene)ethylenediamine as chemosensor for the selective

recognition of acetate and its interaction with cells for bio-

imaging: Experimental and theoretical studies

Received 00th January 20xx,

Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x

a

b

J. Guadalupe Hernández, Carlos Alberto Huerta-Aguilar, Pandiyan Thangarasu,* Herbert

www.rsc.org/

c

Höpfl

1

A ruthenium(III) complex of N,N´-bis(salicylidene)ethylenediamine (L ) was prepared to give a

1

compound of composition [RuL (H

2

O)(PPh

3

)]PF

6

, which was examined by spectroscopic methods

and single-crystal X-ray diffraction analysis. The geometric analysis was accomplished by DFT

studies, which enabled a comparative analysis with related Ru(III) complexes. Sensing studies by

1

+

means of fluorescence spectroscopy revealed that [RuL (H

2 3

O)(PPh )] performs the selective

-

detection of acetate without interference from the presence of other anions (F , Cl , Br , I , CN ,

-

-7

4 3 4 2 4

ClO , NO , HSO , H PO ), with detection limit of 1.20 x10 M. The stoichiometry of the complex

formed between the ruthenium complex and acetate is 1:1, as determined by Job´s method.

Molecular orbital analysis based on DFT calculations revealed that the energy of the orbital, which

1

is responsible for the Photo Electron Transfer (PET) mechanism, is lowered for [RuL (H

2

O)(AcO)]

1

+

2 3

when compared to that for [RuL (H O)(PPh )] , resulting in an enhanced fluorescence intensity

after addition of acetate. Furthermore, the recognition of acetate ion with the ruthenium complex

in Saccharomyces cerevisiae cells was studied, and the absorption of substrate (host) within the

cells, and the subsequent addition of guest (acetate anion) were carefully examined through the

fluorescence.

1

. Introduction

The binding of a receptor with a guest molecule

implies electronic changes in such a way that the

The recognition of ionic or neutral species through

whole unit (Host-Guest complex) can exhibit a

-6 distinct color, a change of the fluorescence or

receptor molecules is an interesting topic because

1

of biological and environmental applications .

alternate redox potential properties; thus,

considerable attention is being given to the

development of molecular-recognition/sensing

7

-12

systems . The main factors altering the spectral

or redox properties are: (i) solvent medium as it

plays a crucial role for ion sensing through

hydrogen bonding interactions between host

1

3-16

molecule and guest

; (ii) ligand attached

covalently to the binding site, since it can facilitate

bond formation between host and guest by means

of variations in size and shape and enable the

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1

7-19

development of a detecting signal

; (iii) the pH significantly involved in various metabolic

of the medium that potentially influences and processes (enzyme activity and antibody functions)

5

9,60

even changes the nature of the electrostatic

.

Acetate possesses unique chemical

interaction between negatively charged anions properties, and can form strong hydrogen-bonding

2

0-22

and positively charged receptor

; (iv) the interactions with a series of different donor

hydrophobic effect, which determines the nature functions such as urea and boronic acid derivatives

6

1,62

of the interaction between the binding site of

.

2

3,24

ligand and the guest in polar solvents

; (v) the

25,26

In this contribution, the recognition of acetate

was studied by means of a ruthenium(III) complex

type of guest ions

.

Metal

complexes

exhibiting

luminescent derived

from

N,N´-

1

properties can be applied as fluorescent bis(salicylidene)ethylenediamine (L ). Salen ligands

27-30

chemosensors for a series of analytes

, and are are versatile for metal complexation and a large

frequently more stable when compared to organic number of derivatives have been prepared by

receptors; moreover, they are susceptible to varying the N−N bridge and introducing

structural changes by altering the metal-to-ligand substituents at the imine carbon or the aromatic

6

3-67

charge transfer (MLCT) or ligand-to-metal charge ring

. The results presented herein show that

1

+

transfer (LMCT) upon the binding process with [RuL (H O)(PPh )] specifically recognizes acetate

2

3

anions. Metal complexes adopting varying ions without the interference of other ions. Since

3

1

structures

exhibit novel redox, spectral, the imine nitrogen is efficiently bonded to the

32

magnetic, luminescence and catalytic properties ; metal ion, the receptor properties of the complex

therefore, they can be employed as versatile for anion recognition can be tuned adequately by

3

3-35

probes for the recognition of anions

. In modifying the donor capacity of the C=N bond.

particular, ruthenium complexes have received DFT studies were employed to illustrate the

great attention because of their intense MLCT enhancement of the fluorescence intensity upon

transitions, interesting photo-physical properties, addition of acetate to the complex in a solvent

enhanced stability (photo-stability), and unique mixture

(H O:CH CN).

Furthermore,

the

2

3

electrochemical behavior. These characteristics recognition of acetate by the ruthenium complex

enable to improve the selectivity in the anion was studied in Saccharomyces cerevisiae cells by

3

6-40

recognition process

, and thus ruthenium means of confocal microscopy analysis, and the

complexes are widely used to study the absorption of substrate (host) within the cells, and

-

recognition of anions, in particular AcO , CN , F , the subsequent addition of guest (acetate anion)

-

41-46

and H

2

PO

4

. The detection of anions is were carefully examined through the fluorescence.

essential as they play vital roles in many chemical,

4

7-58

2. Results and Discussion

biological, and environmental processes

. In

2

.1 X-ray diffraction analysis and DFT studies

addition, many co-factors and other biochemically

relevant substrates are anionic in nature. Thus,

anion recognition is of great interest, as it involves

species being crucial for enzyme activities, the

transport of hormones, protein synthesis and DNA

regulation. Importantly, acetate anions are

The

molecular

O)(PPh )][PF ]}⋅CH

single-crystal X-ray

structure

was determined by

diffraction analysis.

of

1

{

[RuL (H

2

3

6

2 2

Cl

Crystallographic data collection (see experimental

2

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3

section) and selected geometric parameters are the PPh moiety. Due to the bulkiness of the

summarized (see Table 1). The full list of geometric triphenylphosphine ligand, the P1-Ru1-N1, P1-Ru1-

data is given in the Supplementary Material (Table

Table 1. Selected bond lengths [Å] and bond

S1a-d).

angles [°] for the description of the coordination

A perspective view of the molecular structure of

geometry of the ruthenium atoms in

1

+

1

the molecular cation, [RuL (H O)(PPh )] , is given

2

3

{[RuL (H O)(PPh )] PF }⋅0.5CH Cl

2

3

6

2

2.

in Fig. 1a in comparison to the geometry-optimized

structure (Fig. 1b).

Ru1—P1

Ru1—O1

Ru1—N1

2.3409(16)

2.008(4)

2.003(5)

Ru1—O2

Ru1—O3

Ru1—N2

2.006(5)

2.185(5)

1.983(5)

O1—Ru1—P1

O1—Ru1—O3

O2—Ru1—P1

O2—Ru1—O1

O2—Ru1—O3

O3—Ru1—P1

N1—Ru1—P1

N1—Ru1—O1

90.62(14)

87.65(19)

94.13(13)

94.79(19)

84.04(18)

N1—Ru1—O2

N1—Ru1—O3

N2—Ru1—P1

N2—Ru1—O1

N2—Ru1—O2

90.3(2)

90.5(2)

95.07(15)

91.7(2)

1

Fig. 1. (a) Perspective view of [RuL (H

2

O)(PPh

3

)]PF

6

with thermal ellipsoids at the 50% probability level;

b) DFT geometry-optimized structure of

168.69(19)

87.0(2)

(

177.37(14) N2—Ru1—O3

1

+

[

RuL (H

2 3

O)(PPh )] in the gaseous state at B3LYP /

91.37(16)

174.3(2)

N2—Ru1—N1

82.9(2)

DGDZVP level of theory.

1

+

2 3

In the molecular structure of [RuL (H O)(PPh )] ,

N2, P1-Ru1-O1 and P1-Ru1-O2 bond angles of

the central ruthenium (III) ion exhibits distorted

octahedral geometry as illustrated by the bond

angles for the trans-oriented atoms: 177.37(14)°

for O3-Ru1-P1, 174.3(2)° for N1-Ru1-O1, and

9

1.37(16), 95.07(15), 90.62(14) and 94.13(13) °

deviate mostly significantly from 90°, meanwhile

the corresponding bond angles with the water

ligand (O3) are close to 90° or significantly smaller:

1

68.69(19)° for N2-Ru1-O2. The bond angles for

9

0.3(2), 90.5(2), 87.65(19 and 84.04(18)°. The

the cis-oriented substituents vary from 82.9(2) to

geometric data resulting from the structural

9

5.07(15)°, of which the smallest value

analysis are consistent with those reported for

corresponds to the N1-Ru1-N2 bond angle of the

five-membered RuNCCN chelate ring and the

largest to the O1-Ru1-O2 and N2-Ru1-P1 bond

angles: 94.79(19) ° and 95.07(15) °, respectively.

The bond distances formed between the metal

atom and the salen-donor atoms N1, N2, O1, and

O2 with Ru1 are 2.003(5), 1.983(5), 2.008(4), and

68-71

other related ruthenium(III) complexes

.

Interestingly, one of the phenyl groups of the PPh

3

moiety exhibits an intramolecular π−π interaction

with one of the aromatic rings of the salen ligand,

as evidenced by the centroid−centroid distance of

3

.94 Å (Fig. 1a).

2

.006(5) Å, respectively (Table 1), forming the The molecular geometry established by the single-

equatorial plane in the coordination polyhedron. crystal X-ray diffraction analysis was reproduced

The axial bonds (Ru1-O3, 2.185(5) Å; Ru1-P1, by DFT calculations at the at B3LYP / DGDZVP level

2

.341(16) Å) are formed with a water ligand and of theory, giving a coherent data set. Since the

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quantum-mechanical calculations refer to the transition metal ions with salen ligands in

molecule in the gaseous state, the bond lengths dependence of the number of d-electrons.

are increased when compared to the solid-state

In order to analyze the structural variations in

analysis, which was carried out at

T = 100 K. The

dependence of the oxidation state, the complex

geometry was optimized also for the ruthenium

ion (II) analogue. The results given in Scheme 1

show that there are significant differences for the

distances of nitrogen, phosphorus and oxygen

calculated Ru-N and Ru-O bond lengths formed

with the salen ligand are: 2.059/2.040 Å and

2

.049/2.046 Å for Ru1-N1, Ru1-N2, Ru1-O1 and

Ru1-O2, respectively (Scheme 1). The axial bond

lengths for the Ru-P and Ru-O bonds [2.384 for

Ru1-P1; 2.325 Å for Ru1-O ] agree with previously

w

(

water) atoms bonded to the metal ion. The

w

27,71-73

distance of 2.384 Å for the Ru(III)-P was increased

published data

. The bond angles are also

to 2.650 Å for Ru(II)-P. Similarly, the Ru(III)-O

w

well-reproduced with values of 171.50° for N1-

Ru1-O1, 163.79° for N2-Ru1-O2 and 172.86° for

O3-Ru1-P1. The remaining bond angles are in the

range of 78.99° to 98.65°. For comparison, the

bond distances for a series of different transition

metal (III) complexes with salen ligand were

distance is increased from 2.325 to 3.370 Å for

Ru(II)- O

w

.

Since the ruthenium complex performs as chemo-

-

sensor for the detection of AcO ions, the geometry

1

of [RuL (H

2

O)(OAc)] was also optimized, showing

7

0,71,73-78

analyzed

, showing that the M−^Nimine bond

that the Ru-O_A_cbond distance of 1.985 Å is

distance decreases in an approximate linear

tendency with increasing number of electrons in

the d-orbitals (Fig. 2). Similarly, metal (II)

complexes with the salen ligands were also

significantly shorter than the Ru-O

w

bond that

decreased from 2.325 to 2.271 Å. The Ru-O and

Ru-N bond distances with the salen ligand are

shorter when compared to the triphenylphosphine

, obeying the same linear trend with

complex (Scheme 1).

7

9-87

analyzed

increasing number of d-electrons (Fig. 2).

2

1

.35

.30

.25

.20

.15

.10

.05

.00

.95

.90

.85

e

-

Metal

M-N

Mn3+(d

4

)

2.292

2.111

2.011

2.003

1.953

y = -0.0786x + 2.3098

R² = 0.8516

Fe3+(d

5

)

P1

_R_u3+₍_d5₎

Ru³⁺(d⁵)

Co3+(d6

)

imine N2

O1

N1 imine

O2

imine N2

O1

N1 imine

O2

Ru(II)

Ru(III)

H

2

O

2

H O

Mn³⁺(d⁴) Fe³⁺(d⁵) Ru³⁺(d⁵) Ru³⁺(d⁵) Co³⁺(d⁶)

+

CH

3

COO^-

2.30

2.25

2.20

2.15

2.10

2.05

2.00

1.95

1.90

Metal ions

M-N

Mn2+(d

5

)

2.239

2.226

2.071

2.119

2.055

1.956

1.985

y = -0.0471x + 2.2813

R² = 0.8612

Fe²⁺(d⁶

Ru²⁺(d⁶

)

AcO

Co2+(d

7

)

Ni2+(d

8

)

imine N2

N1 imine

O2

Cu2+(d

9

)

Zn2+(d10

)

Ru(III)

O1

2

H O

Mn²⁺(d⁵) Fe²⁺(d⁶)^R^u

2+

(d

6

) Co2+(d

7

)

Ni2+(d

8

)

Cu²⁺(d ) Zn²⁺(d¹⁰

9

)

Scheme 1. Variation of the bond distances (axial

Fig. 2. a) Comparison of the M

−

N

imine bond

and equatorial) upon the change of the oxidation

distance of different a) trivalent and b) divalent

1

state,

([Ru(II)L (H

2

O)(PPh

3

)]

vs.

[Ru

4

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1

+

(

III)L (H

2

O)(PPh

3

)] ) and upon coordination of of electron density in the systems. For example, ƞ

1

acetate in methanol, ([RuL (H O)(AcO)]).

= (LUMO-HOMO)/2 corresponds to the global

hardness (ƞ) of the complex in relation to its

reactivity; the hardness (ƞ=1.466 eV) and softness

values (σ = 1/ƞ = 0.682 eV) for the salen ligand

changed to ƞ = 1.132 and σ = 0.884 eV,

2

The elongation of the axial bond (Ru-P) upon the

reduction of Ru(III) to Ru(II) in the octahedral

structure can be attributed to the Jahn-Teller

effect. Because of the ground state degeneracy of

the complex, it undergoes Jahn-Teller distortion

3+

respectively, after complex formation with Ru in

the gaseous state. For the oxidation state of

1

+

from octahedral symmetry for RuL (H

2

O)(PPh

) (low spin), which destabilizes the metal d-

3

)]

(

Ru(II), the following values were employed: ƞ =

.438, σ =0.695 eV (Suppl. Mat. Table S5).

5

1

(

d

) to tetragonal symmetry for [RuL (H

2

3

)]

1

6

(

2

orbital (dz ). The order of stabilization is:

The following equation was used to calculate ∆E

and µ for the complexes.

1

+

5

1

Ru(III)L (H

2

O)(PPh

3

)] (

d

) ˃ Ru(II)L (H

2

O)(PPh

3

)]

6

(

d

). Furthermore, according to the HSAB concept

Ru(II) prefers to coordinate with soft P1, and

_ꢀꢁ

ꢂꢃ

ꢅꢆꢇ

^aⁿ^d^µ⁼^ꢄ^ꢄ⁻ꢂ

∆

E =

-

w

destabilizes the Ru-O bond, while the hard AcO

ion and water strongly interact with Ru(III).

I= ionization potential (IP); A=electron affinity (EA),

and µ = chemical potential; η= chemical hardness

of the ligand.

The molecular orbital (MO) analysis established

bond formation by showing overlap of the ligand

orbitals with those of the metal. For the ruthenium

The calculated values for

ꢀ

E (∆E = -31.745 for

1

+

(

2 3

III) complex [RuL (H O)(PPh )] , the HOMO

1

[

RuL (H

2

O)(PPh

3

)] and ∆E= -145.045 for

orbitals resulted from the overlap of d[Ru(III)] with

1

+

RuL (H O)(PPh )] ) indicate that the global

2

3

1

the

π

/p orbitals of L , yielding the following

hardness of the complexes decreases with

increasing oxidation state of the metal ion. This

molecular orbitals: HOMO to HOMO-X; X= 0-6, 10,

2) (Suppl. Mat. Table S4 and Fig. S3b). The

1

+

2 3

evidences that [RuL (H O)(PPh )] is more reactive

presence of

π-character of the imine moiety is

than the Ru(II) analogue, which is consistent with

corroborated by the nature of the HOMO and

the reported observation that if η ˃ 0 and ∆E < 0,

other low-lying orbitals (LUMO-x (x=0-2). The

88

charge transfer is energetically favorable

.

2

LUMO orbitals are composed of dz (Ru) and the

Furthermore, for the ligand, the charge

distributions of the imine nitrogen and hydroxyl

oxygen atoms were analyzed, indicating that there

is an excess of electron density on the

heteroatoms facilitating bond formation with the

metal ion (Suppl. Mat. Table S6). This is consistent

with the Mulliken charge analysis, where a

significant change in the charge density of the

orbitals of atoms N(1), N(2), N(12), O(1), O(2) and

P(1), confirming the existence of a Ru-P bond. For

1

the case of [RuL (H

2

O)(AcO)], where PPh

3

is

-

substituted by AcO , the following orbitals: HOMO

to HOMO-X (X= 0-10) (Suppl. Mat. Fig. S3c) were

resulted, and this study was carried out as the

complex selectively recognizes the acetate ion.

The global physical properties of complexes donor atoms was observed after the formation of

1

+

1

[

RuL (H

illustrated by means of the hardness parameter the metal). For the uncoordinated ligand, the

ƞ), which responds to changes of the distribution charge densities were: N1 (-0.347) and N2 (-0.209),

2 3 2

O)(PPh )] and [RuL (H O)(AcO)] were the complex (charge transfer from heteroatoms to

(

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2 2

which changed to -0.315 and -0.308 after complex 791 nm with increasing percentage of CH Cl (25,

formation with Ru(III), indicating charge transfer 50, 75 and 100%). Since the complex recognizes

from the ligand to the metal. Similarly, charge acetate ions in aqueous medium as shown by a

transfer was also observed during the complex comparative analysis (fluorescence characteristics

1

formation of (L ) with Ru(II), i.e., the charges of N1 in the presence of anions), acetate was added to a

(

-0.347) and N2 (-0.209) changed to -0.314 and - solution of the complex to monitor the UV-visible

0

.293 after complex formation.

spectral behavior, giving a significant change in the

intensity of the absorbance (See Fig. 4).

Ligand reactivity:- The reactivity of the ligand was

also analyzed by Hirshfeld and natural population

analysis (NPA), as these methods are effective for

3.50

3

.00

.50

understanding

intra-

and

intermolecular

MeOH(100%)

2

interactions, and play an important role for the

analysis of charge transfer or conjugative

interaction in molecular systems. These

parameters are effective also in analyzing the

molecular geometry, and enable to predict the

mutual orientation of the molecules in the

condensed matter or the nature of atoms

MeOH(75%):CH2Cl2(25%)

MeOH(50%):CH2Cl2(50%)

MeOH(25%):CH2Cl2(75%)

CH2Cl2(100%)

2.00

1

.50

.00

1

0.50

0.00

8

9

exhibiting close contacts . CAFI f(r) data were

calculated by using the B3LYP method with two

different basis sets (6-31G** and DGDZVP) (Suppl.

Mat. Tables S7a and S7b). The results show that

the Hirshfeld population analysis and natural

population analysis (NPA) predict positive values

for all ligand atoms. The Fukui function analysis

indicates that the most reactive sites for

250

350

450

550

650

750

850

950 1050

Wavelength (nm)

1

+

2 3

Fig. 3. Spectral changes for [RuL (H O)(PPh )] in

solvent mixtures of methanol and dichloromethane

with different proportions.

[RuL1(H2O)(PPh3)]+

2

.5

[RuL1(H2O)(AcO)]

-

2

electrophilic attack, f (r) are N1, N2, C1, C2, C7,

C10, C11, C12, O1 and O2, while the most reactive

1.5

1

+

sites for nucleophilic attack f (r) are C3, C4, C5, C6,

C14 and O1.

0.5

2

.2 Electronic spectra

0

250

350

450

550

650

750

850

950

1050

1

+

For RuL (H

recorded in solvent mixtures containing different

proportions between methanol and

dichlormethane (See Fig.3). The absorption bands

2

O)(PPh

3

)] , the electronic spectra were

Wavelength (nm)

Fig.

4

.

Experimental UV-Vis spectrum of

1

+

___

[

343, 497, 740, 917 nm) in methanol show the

RuL (H

2

O)(PPh

3

)]

(0.5 mM) ( ) and after

(

addition of 100 µL of 0.1mM [TBA]OAc to the

existence of a solvent effect, and a red-shift is

complex (----) in CH CN:H O (90:10 %, v/v).

observed in CH

2

Cl

2

. In the presence of CH

2

Cl

2

, the

3

2

values for the absorption maxima are 750, 759 and

6

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To analyze the orbital contributions to the spectral bands at 555.73, 567.04, 639.32, 709.74, 780.51,

bands, the spectra were calculated by TD-DFT 836.71, 960.97, 1018.27 and 1149.49 nm (see

1

calculations using the B3LYP/DGDZVP basis set and Suppl. Mat. Table S4). For [RuL (H

2

O)(AcO)], the

considering methanol as solvent in the PCM HOMO-x (x = 0-10) orbitals are coupled with the

1

+

2 3

model. For [RuL (H O)(PPh )] , the calculated metal LUMO orbitals to exhibit electronic bands at

spectrum agrees reasonably well with the 414.16, 423.08, 432.51, 523.03, 554.99, 681.79,

experimental graph in the low energy band (See 724.71, 861.90, 1493.97 and 1923.43 nm. This

Suppl. Mat. Fig. S4 and S5) (

λexp = 343, 497, 740, indicates that the bands in the visible region are

9

0

9

17 nm; calc = 495, 630 and 808 nm) . The bands derived from an excited state containing mixed

λ

are originated from metal-to-ligand charge Ru(III)-N orbitals, i.e., the HOMO orbitals localized

transfer (MLCT), and were assigned as follows: 343 on the ligand, especially on the imine and hydroxyl

nm for Ru(III)(dπ)→Nimine; 497 nm for PPh

3

(π*) moieties, overlap considerably with the LUMO

2

and 740-917 nm for Ru(III)(dπ)→Owater and orbital (higher-energy dz ) of the metal ion

6

5, 91

O_p_h_e_n_o_l_i_c(π*)

For

.

through MLCT. The shifts of the bands in the

visible region (724.71 and 681.90 nm) are in good

1

+

)] ,

[RuL (H

2

O)(PPh

3

which

recognizes agreement with the experimental value of 740 nm,

specifically acetate, the interaction with that anion showing a difference of 15 and 58 nm. Additional

was also studied. The TD-DFT absorption spectra MLCT transitions are originated from the mixing of

1

+

1

for [RuL (H O)(PPh )] , [RuL (H O)(AcO)] and orbitals HOMO-x (x = 0-10) with the LUMO orbitals

2

3

2

1

[

RuL (AcO)(PPh

3

)] are shown in Fig. S5 and S6 of

dxy character. Furthermore, there is possible

(

[

Suppl.

Mat.). The results show that contribution of the HOMO orbitals (Ru-t ) to p

2

g

1

+

RuL (H

2

O)(PPh

3

)] exhibits a band at 518 nm with (nitrogen imine), as well as an anti-bonding

(PPh ).

a shoulder at 946 nm in the gaseous phase (495, combination of HOMO (t2g) with

30 and 808 nm), and is similar to the

experimental spectrum only in the low energy

p

3

6

9

0

2.3 Selective recognition studies of acetate by

band . On the contrary, the spectrum of

1

+

1

[RuL (H

2

O)(PPh )]

3

[

2

RuL (H O)(AcO)] illustrates a considerable solvent

effect, giving three bands (497, 725 and 1277 nm)

in the gaseous phase, and two bands (557 and 966

nm) in methanol. The bands can be attributed to

Anion binding tests:- The ruthenium complex

1

+

[

RuL (H O)(PPh )] was tested as chemosensor for

2 3

the recognition of anions. For this purpose, the

fluorescence emission was monitored upon

addition of the anion to a solution of the complex.

electron donation from the ligand

σ orbital toward

an empty metal orbital and simultaneous

d

-

electron donation from a filled d orbital to a π*

In the binding tests, a series of anions (F , Cl , Br , I ,

-

anti-bonding orbital of the ligand.

CN , ClO , NO , HSO , H PO ) were explored in

4

3

4

2

4

the form of the tetrabutylammonium salts. For the

1

+

experiment, to [RuL (H

2

O)(PPh

O/CH CN (1:9, v/v), a solution

of the corresponding anion (50 L, 0.1 mM) in the

3

)] (3.0 mL, 0.1

The orbital contributions to the spectral bands

1

+

mM) dissolved in H

2 3

were analyzed. For [RuL (H O)(PPh )] (495, 630

2

3

ꢁ

and 808 nm), the transitions are originated from

the HOMO-x (x = 0 to 6, 10, 12) (Ru-Nimine) orbitals

through overlap with the LUMO orbitals to give

same solvent mixture was added, where after the

fluorescence emission (360-750 nm) was

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measured. A considerable fluorescence response mM) in H

2

O: MeCN (10:90 %), showing that the

was observed only for acetate, indicating that peak intensity increased with increasing

1

+

[

2 3

RuL (H O)(PPh )] performs as chemosensor for concentration of acetate (Fig. 6). In the interval of

the detection of this anion. When the 0.0 mM to 0.015 M the fluorescence emission at

chemosensor complex was exited at 365 nm, a 430 nm increases linearly with increase of the

fluorescent emission signal was observed at 430 concentration of acetate. Above 0.015 M, the

nm. The change in the spectral emission bands change in fluorescence decreases and becomes

(

380 and 430 nm) in the presence of acetate is negligible after 0.025 M. The results suggest that

considerable, when compared to the remaining there is an excited-state interaction between the

anions where only one band with very low receptor and the anion during the interaction.

fluorescence intensity was observed (see Fig. 5).

92

These results indicate that the acetate ion is more Photo-induced electron transfer (PET)

is

suitable to substitute the bulky PPh group in the generally accepted as mechanism for “turn-on”

3

1

+

coordination sphere of the [RuL (H

2

O)(PPh

3

)] fluorescent chemosensor. In the absence of

complex than other anions.

analyte in the “electron donor-acceptor” system,

the HOMO (donor) orbital has higher energy than

that of the acceptor, facilitating the transfer of an

Host

5

4

3

2

1

0

50

.0

.5

45

.0

40

35

.5

Acetate

Chloride

Bromide

Perchlorate

Nitrate

electron to the acceptor’s HOMO, which

diminishes the fluorescence intensity; this

observation is an agreement with the published

.

3

0

Dihydrogen Phospate

Hydrogen Sulphate

Iodide

25

.5

.

2

0

Fluoride

15

.5

.0

10

9

3,94

1

+

.5

5

report

2 3

. Upon excitation of [RuL (H O)(PPh )] ,

.0

0

in the PET process, an electron is transferred from

the HOMO (donor, E = 8.516 eV) to the low-energy

HOMO orbital of the acceptor (fluorophore) and

quenches the fluorescence emission. However,

3

80

400

420

440

460

480

500

520

540

Wavelength (nm)

Fig.5. Change of the fluorescence behavior during

the addition of different anions (0.1 mM) to

1

+

1

+

2 3

when acetate is added to [RuL (H O)(PPh )] , the

[

RuL (H

).

2 3 2

O)(PPh )] (0.1 mM) in H O:MeCN (10:90

receptor HOMO energy (-8.516 eV) is being

lowered to -9.277 eV, inhibiting the photo-

%

The solubility of the Ru complex is an issue as it induced electron transfer, and it leads to enhance

poorly dissolves in 100 % water medium. So we the fluorescence emission (Scheme 2). This

tested the solubility of the complex in different inference agrees with the PET mechanism

9

5, 96

solvent mixtures, founding only in H

2

O/CH

3

CN reported for metal complexes

.

(

10:90 %, v/v) was suitable for the experiments.

1

+

2 3

Titration studies of [RuL (H O)(PPh )] against

acetate: A titration analysis was performed in

order to study the binding behavior of

1

+

[

RuL (H O)(PPh )]

with acetate ions. The

2

3

fluorescence emission intensity was measured

after each subsequent addition of acetate (0.0 to

0

.025 M) to a solution of the complex (2.0 mL, 0.1

8

| J. Name., 2012, 00, 1-3

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500

450

400

350

300

Fig. 6. a) Increase of the fluorescence intensity of a

1

solution of complex [RuL (H

2

O)(PPh

3

)]PF

6

(0.1 mM)

3 2

in CH CN/H O (90:10 %); v/v) at 430 nm during

successive addition of acetate (0.0 - 0.025 M); b)

Plot of fluorescence intensity vs. concentration of

acetate.

250

2

00

50

1

100

50

0

Fig. 7. Sensing of acetate recognition by the

1

+

receptor complex [RuL (H

the presence of an equimolar amount of an

additional anion in CH CN/H O (90:10 %; v/v) by

2 3

O)(PPh )] (0.1 mM) in

3

2

Scheme 2: Illustration of the PET mechanism

measuring the fluorescent emission at 430 nm.

1

+

proposed for the interaction of [RuL (H

2

O)(PPh

3

)]

with acetate

Stoichiometric ratio:- To examine the ratio of the

acetate interaction with the ruthenium complex,

Job’s method was employed. The results showed

that the fluorescence intensity increased

proportionally until ~1.0 equivalents of acetate

were added to the complex, indicating that the

Competitive binding analysis:- The inference of

1

+

other anions on the binding of [RuL (H O)(PPh )]

2

3

with acetate was also analyzed by measuring if

changes in the fluorescence intensity occurred. To

1

+

a solution of [RuL (H

2 3

O)(PPh )] (0.1 mM, 2.0 mL)

stoichiometry

of

+

the

reaction between

and [TBA]OAc (100.0 μL, 100.0 mM) in CH

3

-

CN/H

2

O

-

1

[

RuL (H O)(PPh )] and acetate is 1:1 (Fig. 8).

2 3

-

(

90:10 %; v/v), different anions (F , Cl , Br , I , CN ,

-

4 3 4 2 4

ClO , NO , HSO , H PO ) were added to give a

final concentration of 16.0 mM. After stirring the

resulting mixture for 15 min, the solution was kept

for 5 min. to reach equilibrium, followed by

excitation at 365 nm and measurement of the

fluorescence emission in the visible region. The

results showed no significant changes in the

fluorescence intensity, indicating that there is no

considerable interference from other anions

during the recognition of acetate through

1

+

RuL (H

2

O)(PPh

3

)] (Fig. 7).

Fig.8. Job´s Plot showing that the stoichiometry of

1

+

the complex formed between [RuL (H

2

3

O)(PPh )]

and the acetate ions is 1:1.

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-

The detection limit of the Ru(III) complex for AcO After revising the literature, particularly, for the

-7

was 1.20x10 M, which was determined by 3- detection of anions by different ruthenium

sigma method using the linear regression plot complexes, it evidences that ruthenium complexes

derived from the standard deviations of the are capable to detect selectively anions such as

9

7, 98

-

experimental data (see Suppl. Mat. Fig. S7)

. CH

3

COO , F , Cl , CN , NO

3 2 4

and H PO (see Table 2).

-1

Limit of detection (LOD) = 3σs ; σ= standard

deviation of response; s= slope of the calibration

curve.

-

2

.4. Theoretical analysis: Interaction of AcO

1

+

with [RuL (H O)(PPh )]

2

3

The substitution of PPh

3

with acetate in

pH effect:- The behavior of the fluorescence

1

+

1

+

[

RuL (H O)(PPh )] was also analyzed by using DFT

2 3

intensity of [RuL (H

2

O)(PPh

3

)] (0.1 mM, 2.0 mL)

calculations at the B3LYP/DGDZVP level, and

compared the molecular structures of

O)(OAc)]. The

results show that the elongated octahedral

was analyzed also during the addition of NaOH

(

100.0 μL, 1.0 mM). The measured fluorescence

1

+

1

[

2 3 2

RuL (H O)(PPh )] and [RuL (H

intensities were plotted against the pH values,

yielding a straight line (Fig. 9). The fluorescence

intensity decreased at high pH values, it means

that hydrogen bond induced π-electron

1

+

geometry of [RuL (H O)(PPh )] is compressed

2

3

when the voluminous PPh

3

group is replaced by

acetate in the metal coordination sphere (vide

N–H

delocalization

or

anion

induced

supra). This is consistent with the calculated

deprotonation greatly depends on the acidity of

N–H (receptor) as it changes the photophysical

properties of the receptor. At high pH, electron is

being transferred from the lone pair of imine

nitrogen to the photo-excited fluorophore;

consequently, it quenches the fluorescence

intensity, so the protonation of the complex

influences strongly the fluorescent behavior.

2

energy (-6.25 eV) for the d

z

orbitals of

1

+

[

RuL (H O)(PPh )] when compared to -5.26 eV of

2 3

1

2

compressed [RuL (H O)AcO]. Furthermore, the

HOMO-LUMO band gap of 2.26 eV for

1

+

[

RuL (H

2

O)(PPh

3

)]

decreases to 1.62 eV for

1

RuL (H

O)AcO]. As expected, the hardness

1

+

parameter (ƞ) obtained for [RuL (H

2 3

O)(PPh )]

(

1.132 eV) decreases to 0.810 eV for

1

600

550

500

450

400

350

300

[RuL (H O)AcO)] (Scheme 3 and Fig. 10).

2

y = -2.0088x + 54.249

R² = 0.8677

P1

AcO

N1 imine

imine N2

O1

N1 imine

imine N2

O1

AcO^-

Ru⁽^I^I^I⁾

Ru(III)

O2

2

O2

2

dx -y = -4.48 eV

dx -y = -7.66 eV

H O

2

H

2

O

2

dz = -5.26 eV

dz = -6.25 eV

0

1

2

3

4

5

6

7

8

9

10

1

+

1

[

RuL (H O)(PPh )]

[RuL (H O)(AcO)]

2

3

pH

Fig. 9. Plot of fluorescence intensity vs. pH upon

Scheme 3. Variation of the bond distances and

addition of NaOH (100.0 μL, 1.0 mM) to a solution

2

2 2

energy values of the d

z

and dx -y orbitals in the

molecular structures of

RuL (H O)(PPh )] and ([RuL (H O)(AcO)]).

1

+

of [RuL (H

2 3

O)(PPh )] (0.1 mM, 2.0 mL) in

calculated

H

2

O:MeCN(10:90%).

1

+

1

[

2

3

2

1

0 | J. Name., 2012, 00, 1-3

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2

.5 Toxicity Studies

ruthenium complex followed by acetate ion. This is

consistent with the previous observation that the

interaction of the complex with acetate enhances

the fluorescence intensity. Still, more number of

bright images within the cell might be expected if

acetate and the complex were interacted

adequately within the cell. It appears that the size

of the complex plays an important role, i.e. small

molecule like acetate easily enters into cell

through membrane in contrast to the complex as

the larger size, and rigidity of the Ru-complex

hindered the cell permeability; consequently, the

interaction between acetate and the complex is

In order to explore potential applications, the

recognition of acetate ion with the ruthenium

complex in Saccharomyces cerevisiae cells was

studied. The fluorescence responses for the

complex in the presence and absence of acetate

(

450 to 500 nm) were monitored in an Olympus

FV1000 equipment using a 405 nm diode laser as

excitation source. The interaction studies with the

cells were performed in modified Mueller Hinton

agar (Sigma Aldrich) containing meat peptone (2.0

%

22

, Sigma Aldrich) and sucrose (2.0 %, C12H O11).

The absorption of substrate (host) within the cells,

and the effects resulting from the subsequent

addition of guest (acetate anion) were carefully

examined by means of confocal microscopy

analysis to analyze the cell performance.

expected

to

less

within

the

cell.

Saccharomyces cerevisiae cells were obtained from

commercially available yeast culture. In the first

step, the yeast powder (100 mg) was dissolved in

aqueous sucrose solution (3.0 mL, 5.0% w/v) to

allow the cells to grow for 3 hours at room

temperature. This cell culture (100 μL) was

inoculated into Petri dishes containing modified

Mueller Hinton agar to which previously the

testing compounds (ruthenium complex, and their

combinations) had been added. After incubation at

2

5 °C overnight, the systems were analyzed by

confocal microscopy.

In the confocal microscope, Saccharomyces

cerevisiae cells (∼10 um) were observed as round

shaped cells in form of individual cells and

agglomerates (Fig. 11). After excitation at 405 nm,

as expected, no fluorescent response was

observed (Fig. 11). The ruthenium complex was

added as growth factor, no fluorescence (very few

fluorescence dots) was observed. In contrast,

bright spots of the fluorescent signals were

detected within the cells after addition of the

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Table 2. Fluorescence data of ruthenium complexes employed for the detection of anion

Ruthenium complexes

Excitation

wavelength

Emission

(nm)

Detection

Ref.

(

nm)

1

+

1

-

(

[Ru(L )(H

2

O)(PPh

3

)] , L =N,N´-Bis

365

430

603

AcO

This

work

salicylidene)ethylenediamine

-

98

38

[

Ru(bpy) L](ClO ) , L=2-(2-methoxyphenyl)-1H-

456

AcO

2

4 2

imidazo[4,5-f][1,10]phenanthroline

-

[

Ru(bpy) L](ClO , L=2-(2-methoxyphenyl)-1H-

2

4

)

2

456

603

AcO

imidazo[4, 5-f][1,10] phenanthroline

+

-

[

Ru(bpy)

2

(H

3

L)] , (H

3

L=5-(1H-benzo[d]imidazol-2-

498-538

716-760

F and AcO

yl)-1H-imidazole-4-carboxylic acid)

−

-

99

[

Ru(bpy) (L)](PF ) , L=calixarene

458

-

642

615

CN and AcO

2

6 2

-

100

Ferrocene-imidazophenanthroline-based

ruthenium(II)–polypyridyl complex

Cl

−

101

102

Ru(bpy)

2

[4-(2,2-bipyridin-4-yloxy)phenol]Cl

](ClO ; bpy =2,2′-bipyridine

(mpipH)](ClO ; bpy=2,2′-bipyridine,

2

468

450

458

600

593

NO

3

−

[

Ru(bpy)

3

4 2

)

CN

-

2

4

)

2

CN

mpipH=2-(4-methylphenyl)imidazo[4,5-f]-1,10-

phenanthroline

-

102

[

Ru(bpy)

2

(dmpipH)](ClO

4

)

2

; bpy=2,2′-bipyridine

459

596

CN

Dmpiph=2-(2,6-dimethylphenyl)imidazo-[4,5-f]-

,10-phenanthroline

1

-

102

[

Ru(bpy)

2

(mopipH)]-(ClO

4

)

2

; bpy =2,2′-bipyridine;

462

456

461

593

CN

mopipH=2-(4-methoxylphenyl)-imidazo[4,5-f]

[

1,10]phenanthroline

4 2

Ru(bpy) (pmpipH)](ClO ) , bpy=2,2′-bipyridine,

2

CN

pmpipH=2-(pentamethylphenyl)imidazo[4,5-f]-

,10-phenanthroline

1

−

[

Ru (bpy) (mbpibH )](ClO ) ; bpy=2,2′-bipyridine,

CN

2

4

2

4 4

mbpibH =1,3-bis([1,10]-phenanthroline-[5,6-

2

d]imidazol-2-yl)benzene

Page 13 of 21

Journal Name

(tpy)Ru(tpy-HPhImz-Anq)](ClO ) , (tpy)=2,2′:6′,2″-

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−

103

[

488

496

653

658

CN

4

2

terpyridine, (tpy-HPhImz-Anq)=2-(4-(2,6-

di(pyridine-4-yl)phenyl)-1H-anthra[1,2-

d]imidazole-6,11-dione

−

CN

103

[

2 4 2

Ru(tpy-HPhImz-Anq) ](ClO ) ; (tpy)=2,2′:6′,2″-

Terpyridine, (tpy-HPhImz-Anq)=2-(4-(2,6-

di(pyridine-4-yl)phenyl)-1H-anthra[1,2-

d]imidazole-6,11-dione

-

104

103

[

Ru(bpy)2-n(Hdpa)](ClO

4

)

2

; bpy=2,2´-bipyridine,

450

456

490

630

670

679

F and CN

Hdpa=2,2´-dipyridylamine n =1-3

-

[

Ru(bpy)(Hdpa)

2

](ClO

4

)

2

; bpy=2,2´-bipyridine,

F and CN

Hdpa=2,2´-dipyridylamine

−

[

(

(H

2

pbbzim)Ru(tpy-HPhImz-Anq)](ClO

4

)

2

;

CN and

-

2 4

H PO

tpy)=2,2′:6′,2″-Terpyridine, (tpy-HPhImz-Anq)=2-

4-(2,6-di(pyridine-4-yl)phenyl)-1H-anthra[1,2-

d]imidazole-6,11-dione

1

+

1

Fig.10. Comparative molecular orbital analysis of [RuL (H O)(PPh )] and ([RuL (H O)(AcO)])

2

3

2

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Fig. 11. Confocal microscopy analysis of Saccharomyces cerevisiae cells: Optical microscopy under visible

3

+

3+

light (a to c): a) control; b) with Ru complex; c) with Ru complex and acetate. Confocal images upon

3

+

3+

excitation: 405 nm; emission:450-550 nm (d to f): d) control; e) Ru complex; f) Ru complex-acetate.

compounds studied herein by using TMS and

H PO as internal standards. A GC-MS (Joel JMS-

3

. Experimental

3

4

Axsosha instrument) was employed for the

analysis of the mass spectral fragments of the

compounds. UV-vis absorption spectra were

measured with a spectrophotometer from Perkin

Elmer (Lambda 25), and for the fluorescence

studies, a F96 Pro spectrophotometer was used.

3

.1 General information

All chemicals (analytical grade) were purchased

from Sigma-Aldrich and used as received without

any further purification. Elemental (C, H, N)

analyses were performed on an elemental analyzer

(

Fisons instrument, model EA 1108 CHNSO). A

Varian Gemini NMR equipment (300 MHz) was

1

13

31

used to record H, C and P spectra for the

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1

3

.2. Synthesis of the ligand (L )

3.4 X-ray diffraction analysis of {[RuL (H

2

O)(PPh

3

)]

PF

6 2 2

}⋅0.5CH Cl

The preparation of the ligand was achieved by

6

3,64,105

adopting the reported procedure

.

Ethylenediamine (0.60 g, 1.0 mM) dissolved in

EtOH (8.0 mL) was added dropwise to

salicylaldehyde (0.24 g, 2.0 mM) dissolved in EtOH

Single crystals of the title compound were grown

from a solution in dichloromethane. Single-crystal

X-ray diffraction studies were carried out on an

Agilent Technologies SuperNova diffractometer

(

12 mL). The resulting mixture was stirred at room

temperature for hours under nitrogen

atmosphere, whereupon the solution was kept at

2

equipped with a CCD area detector

Mo-Kα radiation ( = 0.71073 Å) (Table 3). Frames

= 100 K. The measured

(EosS2) using

λ

4

°C for 24 hours. The yellow solid formed was

were collected at

T

2

filtered and washed several times with diethyl

intensities were reduced to

F

and corrected for

spherical harmonics

CryAlisPro) . Intensities were corrected for

1

ether. Yield: 0.20 g, 75%. H NMR (300 MHz,

absorption

using

1

07

CD

3 2

OD): CH -N (4H, s, 3.87), N=CH (2H, s, 8.60),

(

aromatic H (8H, m, 7.21), phenolic OH (2H, s,

Lorentz and polarization effects. Structure

solution, refinement, and data output were

1

3.36).

.3 Synthesis of [RuL (H

1

08

performed with the OLEX2

program package

1

3

2

O)(PPh

3

)]PF

6

109

using SHELXL-2014

for the refinement. Non-

The preparation of the ruthenium complex was hydrogen atoms were refined anisotropically. All

1

06

carried out as indicated in the literature . To a hydrogen atoms were placed in geometrically

1

methanolic solution of L (0.27 g, 1.0 mM, 50 mL) calculated positions using the riding model. The

-

was added [RuCl (PPh ) ] (0.96 g, 1.0 mM). The PF counterions are disordered over three

2

3 3

6

resulting solution was refluxed for 5 h and then positions, while the CH Cl solvate molecules are

2

cooled to room temperature. The solvent was located at crystallographic inversion centers. For

roto-evaporated to yield a residue, which was the refinement of the disorder, the PART, SAME,

washed with diethyl ether. A dark green product SIMU, DELU, and SUMP instructions implemented

was obtained, which was recrystallized from in the refinement program were employed. For

methanol: Yield (0.18 g, 23%). Elemental analysis: the CH Cl molecules, the C-Cl bond length was

2

calcd. C H F N O P Ru (792.63): C 51.52%, H fixed to 1.75(1) Å for the refinement. The

3

4 31 6 2 3 2

3

.94%, N 3.53%; observed: C 51.63%, H 3.47%, N geometrical data presented in Table 3.

+

.45%. MS (FAB, m/z (%)): 630 (34%) [M-H

2

O] Crystallographic data for the crystal structure have

] , 263 been

deposited with the Cambridge

Ru] . Crystallographic Data Centre as supplementary

-N (4H, s, 3-15- publication no. 1546463. Copies of the data can be

.81), N=CH (2H, s, 8.36-8.52), Harom (8H, m, 7.38- obtained free of charge on application to CCDC, 12

+

[

(

C

34

H

29

N

2

O

2

PRu] , 154 (100%) [C

8

H

11NO

2

+

22%) [C

9

H

10

N

2

ORu] , 367 (12%) [C16

H

14

N

2

O

2

1

3 2

H NMR (300 MHz, CD OD): CH

3

7

1

3

.74), RuOH (2H, s, 10.24-10.69). C NMR (300, Union Road, Cambridge CB2 1EZ, UK (fax:

2

MHz, CD

phenyl rings and PPh

300 MHz, CD OD): 37.69 (PF

3

OD): CH

2

-N (39.35-40.61), N=CH (157.50), (+44)1223-336-033;

e-mail:

31

3

(129.1-133.47). P NMR deposit@ccdc.cam.ac.uk,

-

(

3

6

), 44.86 (PPh

3

).

http://www.ccdc.cam.ac.uk).

J. Name., 2013, 00, 1-3 | 15

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New Journal of Chemistry

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DOI: 10.1039/C7NJ01591G

ARTICLE

Journal Name

Table

3

.

Crystallographic

)] PF 0.5CH Cl

data

for

1

{

[RuL (H

2

O)(PPh

3

6

}

⋅

2

3

.5

Anion

3

O)(PPh )]

recognition

+

studies

with

1

[

RuL (H

2

0

31 6 2 3 2

(C34H F N O P Ru),

Empirical formula

.5CH Cl

2

For the recognition experiments anion binding

tests, competitive binding (inference) studies, and

titration studies were performed. All experiments

were carried out in triplicate at room temperature.

Formula weight

1670.16

Triclinic

P-1

Crystal system

Space group

For the anion binding analysis, to a standard

a/Å

b/Å

c/Å

α/°

β/°

γ/°

9.7679(2)

1

solution of [RuL (H

2

3 6 3 2

O)(PPh )]PF in CH CN/H O

13.1943(5)

15.3233(6)

67.616(4)

73.070(3)

70.037(3)

(

90:10 %;

v

/v),

a fixed amount of the

corresponding tetrabutylammonium (TBA) salt (0.1

mM) was added, whereupon the fluorescence

properties were analyzed by monitoring the

change of the fluorescence spectral profile for

3

Volume/Å

1686.56(12)

1

+

[

RuL (H

2 3

O)(PPh )] . The titration studies with

Z

TBA]OAc were performed by continuous addition

3

ρcalcg/cm

1.644

0.712

844.0

of the acetate salt to a 10 mL volumetric flask

containing a standard solution of the receptor

-1

μ/mm

F(000)

Crystal size/mm

Θ range for data collection/°

1

+

[RuL (H O)(PPh )] (0.1 mmol), monitoring the

2

3

variations of the fluorescence intensity. The

stoichiometry of the host-guest complex with

0.2 × 0.1 × 0.1

5.18 to 50.00

2

1

10,111

acetate was examined by Job’s method

, for

-

11 ≤ h ≤ 11, -15 ≤ k ≤ 15,

18 ≤ l ≤ 18

Index ranges

which a set of solutions having a constant total

1

2 3 6

concentration of the receptor [RuL (H O)(PPh )]PF

Reflections collected

21886

and the anion were prepared. The stoichiometry of

the complex corresponds to the maximum

obtained in the plot of fluorescence intensity vs.

Independent reflections

Data/restraints/parameters

5930 [Rint = 0.0437]

5930/642/590

1.194

2

Goodness-of-fit on F

-

[

AcO ]/{[AcO ] + [Ru complex]}. The sensing

1

R

1

= 0.0737, wR

2

=

2 3 6

capacity or sensitivity of [RuL (H O)(PPh )]PF as

Final R indexes [I>=2σ (I)]

0

.1785

receptor for acetate anions was studied in a

competitive medium containing the receptor (0.1

mmol), acetate (0.1 mM) and an additional anion

at the same concentration.

R = 0.0768, wR =

1

2

Final R indexes [all data]

0

.1813

-3

Largest diff. peak/hole/eÅ

2.23/-1.33

Computational Procedure

1

DFT calculations were performed for L as well as

1

for

the

complexes

[Ru(II)L (H

2

O)(PPh

3

)]

,

1

+

1

[

Ru(III)L (H

2

O)(PPh

3

)] , [Ru(III)L (H

2

O)AcO], and

1

6 | J. Name., 2012, 00, 1-3

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Page 17 of 21

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NP lee wa s eJ od uo r nn oa tl aod fj uC s ht em ma ri sg it nr sy

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DOI: 10.1039/C7NJ01591G

ARTICLE

1

112

ꢈ^ꢑꢉꢊꢋ ≈ ꢌ_ꢒ_ꢐ_ꢏ_ꢐꢉꢊꢋ

[

Ru(III)L (PPh

3

)(AcO)] using Gaussian-09 . The

exchange correlation was treated with the B3LYP

1

13,114

ꢓ

functional

combined with the DGDZVP basis

ꢈ ꢉꢊꢋ ≈ ꢔꢄꢌ_ꢒ_ꢐ_ꢏ_ꢐꢉꢊꢋ + ꢌ_ꢍ_ꢎ_ꢏ_ꢐꢉꢊꢋꢕꢄꢄꢄꢄ

2

1

15

set . The structure of the ligand was fully

optimized, whereupon the data were used as input

+k

-k

°k

The indexes f , f and f correspond to the

1

23

condensed Fukui indexes

of

with taking the finite

for

the

geometrical

optimization

1

+

difference approximations from the population

analysis of atoms in molecules, depending on the

direction of the electron transfer.

[

RuL (H O)(PPh )]

and the remaining Ru

2

3

complexes. The calculations enabled to determine

the energies of the frontier molecular orbitals, viz.,

the highest occupied molecular orbitals (HOMOs)

and the lowest unoccupied molecular orbitals

For the case of an electrophilic attack, the

following equation is considered:

(LUMOs). The charge distribution in the structures

ꢑ

was analyzed by Natural Population Analysis

ꢄꢈ = ꢔꢗ ꢄꢉꢘꢋ − ꢗ ꢄꢉꢘ − 1ꢋꢕ

ꢖ

89,116,117

(

NPA)

.

For a nucleophilic attack, this equation is applied:

For the determination of the reactive sites of the

ligand, several local and global descriptors

commonly used for organic molecules were

ꢆ

ꢄꢄꢄꢈ = ꢔꢗ ꢄꢉꢘ + 1ꢋ − ꢗ ꢄꢉꢘꢋꢕ

ꢖ

ꢄꢄꢗ = chargeꢄonꢄatomꢄxꢄinꢄtheꢄmolecule

ꢖ

1

18-122

1

considered

. The local reactivity of ligand L

ꢜ

ꢝ

ꢚ ꢆꢚ

ꢛ

ꢓ

ꢛ

was analyzed by using the condensed-to-atom For the attack by a radical, ꢄꢄꢈ = ꢙ

ꢞ is

ꢖ

ꢂ

Fukui indexes (CAFI) f(r), as suggested in the

considered.

1

19,123,124

literature

, and the Hirshfeld charge was

4

. Conclusions

used to calculate the CAFI, yielding reliable NPA

charges. The Fukui function f(r) is a derivative of

the electronic density ρ(r) with respect to the

number of electrons N at a constant external

potential v(r), and, thus, allows in identifying the

most active sites in the ligand:

The structure of a ruthenium(III) complex based on

the N,N´-bis (salicylidene)ethylenediamine ligand,

1

[

Ru(L )(H

2

3

O)(PPh )]PF

6

, was analyzed by single-

crystal X-ray diffraction analysis and DFT

calculations. The results show that the Ru-P bond

distance with the axial-oriented PPh ligand within

3

the distorted octahedral ruthenium complex varies

according to the different oxidation states of the

]

metal

ion,

obeying

HSAB

theory.

If the effect of relaxation for the addition or

removal of electronic charges on the molecule was

not considered, then the following equations were

1

[

Ru(L )(H

2

O)(PPh

3

)]PF was employed furthermore

6

as chemosensor for the selective recognition of

acetate, showing that the fluorescence intensity

increased with increasing concentration of acetate

without showing interference from other anions.

The stoichiometry for the binding of acetate with

the ruthenium (III) complex was 1:1. Furthermore,

the coordination of acetate occurred via

applied by considering

the first unoccupied molecular orbital and

as the density of the highest occupied molecular

ρLUMO(r) as the density of

ρ

HOMO(r)

1

25

orbital

.

ꢈ^ꢆꢉꢊꢋ ≈ ꢌ_ꢍ_ꢎ_ꢏ_ꢐꢉꢊꢋ

displacement of PPh in the axial position, which

3

J. Name., 2013, 00, 1-3 | 17

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ARTICLE

Journal Name

7

V. Amendola, M. Bonizzoni, L. Fabbrizzi Ion Translocation

within Multisite Receptors, 2011.

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0 J. M. Lloris, R. MartínezꢀMáñez, M. E. PadillaꢀTosta, T.

was explored by theoretical calculations. In

addition, the calculations enable to illustrate why

the fluorescence characteristic of the metal

complex changes upon coordination. The energy

of the HOMO orbital is lowered when acetate is

coordinated to ruthenium, thus enhancing the

8

9

1

Pardo, J. Soto, P. D. Beer, J. Cadman, D. K. Smith, J. Chem. Soc.

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3 F. W. Kotch, V. Sidorov, Y. F. Lam, K. J. Kayser, H. Li, M.

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3

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15 P. A. Gale, Acc. Chem. Res., 2006, 39, 465.

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1

into the cells, and in the presence of acetate MartínezꢀMáñez, J. V. RosꢀLis, J. Soto, J. Org. Chem., 2010, 75,

2

1

922.

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0 B. K. McMahon, D. Parker, RSC Adv., 2014, 4, 37649.

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Acknowledgements

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The authors acknowledge Asuntos del Personal 23 A. Chakraborty, R. Gunupuru, D. Maity, S. Patra, E. Suresh,

P. Paul, Inorg. Chem. Commun., 2010, 13, 1522.

Académico (Project PAPIIT No. IN209616) for

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4 L. E. SantosꢀFigueroa, M. E. Moragues, M. M. M. Raposo, R.

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acknowledge USAI (Unidad de Servicios de Apoyo a

la Investigación, Facultad de Química, UNAM) for

7

2

179.

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A ruthenium(III) complex derived from: N, N ′-bis(salicylidene)ethylenediamine as a chemosensor for the selective recognition of acetate and its interaction with cells for bio-imaging: Experimental and theoretical studies

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