Synthesis, structure, and photophysical and electrochemical properties of Ru(ii) complexes of arylene-vinylene terpyridyl conjugates

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Synthesis, Structure, Photophysical and Electrochemical

Properties of Ru(II) Complexes of Arylene-Vinylene Terpyridyl

Conjugates

Received 00th January 20xx,

Accepted 00th January 20xx

Amit Sil,^aSabyasachi Roy Chowdhury,^aSabyashachi Mishra*^aand Sanjib K. Patra*^a

DOI: 10.1039/x0xx00000x

A series of arylene-vinylene π-conjugated terpyridyl ruthenium(II) complexes, [Ru(PPh₃)₂Cl(tpy-C₆H₄-CH=CH-Ar)][PF₆] (1-4;

tpy = 2,2':6',2''-terpyridyl where Ar = phenyl, tolyl, 1-naphthyl and 9-anthracenyl as substituents on 4′ position of tpy) have

been synthesized and characterized by multinuclear NMR, IR, HRMS and single crystal X-ray crystallography. The influence

of the electronic nature of arylene groups on the photophysical and electrochemical properties have been investigated to

understand the electronic interaction between the metal-organic redox centers. Furthermore, σ-donor phenylacetylide

group has been incorporated to accomplish [Ph-C≡C-Ru(PPh₃)₂(tpy-C₆H₄-CH=CH-Ar)][PF₆] (5-8) complexes by the

substitution of coordinated chloride ligand to investigate the change in the redox and photophysical properties. The DFT

studies have been performed to gain an insight into the electronic properties by determining the HOMO-LUMO energy

levels and frontier molecular orbitals for all the synthesized Ru(II) complexes.

www.rsc.org/

because of their attracting photophysical, electrochemical and

catalytic properties.³Furthermore, 2,2':6',2''-terpyridine based

transition metal complexes offer significant advantages such as

Introduction

Mono- and poly-nuclear redox active metal complexes bonded

with extended π-conjugated ligand have attracted much

attention for their potential applications in molecular

electronics.¹The introduction of metal center to organic

molecular π-conjugated scaffolds modifies the chemical,

optical, magnetic as well as the physical properties of the

respective compounds. Moreover, the electronic structure of

the π-conjugated functional groups play a crucial role for

tuning the electronic properties of the molecular wire like

complexes.²Electroactive end-groups and their electronic

nature can modulate the electron transfer of these redox

active organometallic complexes in conjunction with the π-

conjugated functional groups.²Nitrogen containing

long lived excited states, high chemical and photochemical

stabilities and tunability of the excited state energies.⁴In

particular, 2,2':6',2''-terpyridine and its Ru(II) complexes are in

great choice for its wide range of application including catalytic

systems,⁵dye-synthesized solar cell,⁶organic light-emitting

devices (OLED),^3b,7nonlinear optically active systems,⁸mixed-

valence chemistry⁹and electrochromic devices.¹⁰

In the family of terpyridyl ligands, arylene-vinylene

terpyridyl conjugates are attractive functional tridentate

ligands for its interesting photophysical properties as

developed quite recently.¹¹Studies of the excited state

behaviors of this category of push-pull conjugated ligand

systems can be applied for the development of highly

heterocyclic

ligands

such

as

2,3,5,6-tetrakis(2-

luminescent materials^11b,d

,

nonlinear optically active

pyridyl)pyrazine,^2o1,3-bis(2-pyridylimino)isoindolate,^2c1,3,6,8-

tetrakis(1-butyl-1H-1,2,3-triazol-4-yl)pyrine^2d,eand 2,2':6',2''-

terpyridines^1e,p,2a-ghave been utilized for the development of

mono- and binuclear Ru(II) metal-organic electrophores to

study their potential applications in molecular electronics.

Among them, 2,2':6',2''-terpyridine and their structural

analogs have been the focus of intensive research interest

materials^11e-gand fluorescent chemosensors^11a-c. We have

recently reported the arylene-vinylene conjugated terpyridyl

ligands that can act as unique class of fluorescent turn off

sensor for nitroaromatics.^11aIn this context, we have chosen a

series of push-pull terpyridyl conjugates to accomplish the

corresponding

Ru(II)

complexes

as

metal-organic

electrophores. The arylene-vinylene terpyridyl Ru(II)

complexes capped with phenylacetylide termini have also

^a.Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur been introduced in this work to understand the influence of σ-

721302 (India); E-mail: skpatra@chem.iitkgp.ac.in

†Electronic Supplementary Information (ESI) available: Spectroscopic

donor π-conjugated ligand on the redox and photophysical

properties. Their electrochemical properties have been

demonstrated by cyclic voltammetric and differential pulse

voltammetric techniques in order to investigate the influence

of the substituents on their electrochemical properties.

characterization of the synthesized compounds, experimental details,

crystallographic data, selected photophysical data, electrochemical and theoretical

studies. See DOI: 10.1039/x0xx00000x

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pad of celite. After removing all the volatilities under reduced

pressure the solid residue was dissolved in minimum amount

of distilled methanol and was further treated with two

equivalent of NaPF₆. Analytically pure cationic Ru(II) complexes

Results and discussion

Synthesis and characterization

A series of arylene-vinylene conjugated terpyridines (tpy-C₆H₄-

CH=CH-Ar; Ar = phenyl, tolyl, 1-naphthyl and 9-anthracenyl)

were used varying the electron donating nature of the arylene

groups to tune their photophysical and electrochemical

properties. The arylene-vinylene conjugated terpyridines were

accomplished by Wittig condensation between aryl aldehyde

and 4-(2,2':6',2''-terpyridyl-4')-benzyl triphenylphosphonium

(

1-

4)

were obtained with high yield (79-89%) after

subsequently washing with copious amount of diethyl ether. In

¹H NMR spectra of the Ru(II) complexes, the protons adjacent

to the nitrogen atom of the pyridine ring resonates in the

region of 9.04-9.06 ppm with a downfield shift by about 0.18

ppm with respect to free arylene-vinylene conjugated

terpyridines (8.74-8.88 ppm). The other aromatic protons

resonate in the region of 7.08-8.45 ppm whereas the aromatic

protons for the free ligands resonate at 6.98-8.76 ppm. The

bromide in presence of t-BuOK

by following

the literature procedure (ESI).¹¹The luminescent arylene-

vinylene conjugated terpyridines were purified by passage

through silica gel column chromatography (60-120) using ethyl

aromatic carbons of the cationic Ru(II) complexes

(1-4)

acetate and hexanes as eluent to achieve pure L1-L4 (tpy-C₆H₄-

resonate in the region of 120.1-158.3 ppm whereas the

aromatic carbons of the free arylene-vinylene conjugated

terpyridines resonate at 115.3-156.6 ppm. ³¹P {¹H} NMR shows

a sharp singlet at 20.0-20.1 ppm confirming the presence of

two coordinated PPh₃group having similar coordination

environment. In FTIR spectra of the complexes (1-4), the

CH=CH-Ar; Ar = phenyl, 4-tolyl, 1-naphthyl, and 9-anthracenyl)

which are unambiguously characterized by multinuclear NMR

and HRMS (ESI⁺) analyses (ESI). The arylene-vinylene

conjugated terpyridines show two doublets between 6.96-7.34

ppm with coupling constants with J ≥ 16.0 Hz confirming the

trans-vinylene linkage. The attracting redox nature of the

ruthenium(II)-polypyridyl complexes prompted us to

incorporate Ru(II) metal fragments to the arylene-vinylene

conjugated terpyridyl ligands. In order to synthesize the

organic-inorganic hybrid electrophores [RuCl(PPh₃)₂(tpy-C₆H₄-

-

strong band at 843 cm^-1validates the presence of PF₆as a

counter anion. Finally, all the arylene-vinylene conjugated

terpyridyl Ru(II) complexes (

(ESI⁺), revealing the molecular ion peaks for [M-PF₆]⁺at m/z=1

of 1072.2383, 1086.2477, 1122.2493 and 1172.2686

respectively. The isotopic distribution pattern for the

molecular ion peaks of complex obtained from the

1-4) were characterized by HRMS

CH=CH-Ar)][PF₆] (1 ),

-

4

arylene-vinylene

conjugated

terpyridines (L1-L4) were refluxed with [Ru(PPh₃)₃Cl₂] in

1-4

degassed methanol under an inert atmosphere. The reddish

brown reaction mixture was subsequently filtered through a

experimental data are in perfect agreement with the simulated

data for all the Ru(II) complexes as shown in Fig.1.

Scheme 1. Synthetic route for Ru(II) complexes (1-8) (Yield in parentheses).

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phenylacetylide capped Ru(II) complexes

(

5-8

)

were

characterized by HRMS analyses showing molecular ion peaks

([M-PF₆]⁺) at 1138.2987, 1152.3149, 1188.3170 and

1238.3377 respectively with perfect arrangement in the

isotropic distribution pattern to the simulated values (ESI).

Solid state structure

Single crystals suitable for X-ray analysis of the Ru(II)

complexes (1-3) were grown by layering hexanes on DCM

solution of the respective Ru(II) complexes. Interestingly, the

Ru(II) complexes were crystallized as chloro-bridged dimers,

[Ru₂(PPh₃)₂(µ-Cl)₂(tpy-C₆H₄-CH=CH-Ar)₂]²⁺(Ar

=

phenyl, 1-

napthyl) (1′ and 3′

)

in the crystallization medium. During

crystallization, dissociation of one PPh₃ligand leads to the

formation of coordinatively unsaturated intermediate Ru(II)

complexes. Consequently, the chloro-bridged coordinatively

saturated dimeric Ru(II) complexes were crystallized out as

obtained from its solid state structures (Fig. 2). The two Ru(II)

centers of both the complex 1′ and 3′ are bridged by two

chlorides. For complex 1′ and 3′, the Ru1−Cl1-Ru1_i angles are

97.5(9)° and 100.1(9)° respectively whereas Cl1−Ru1−Cl1_i

angles are found to be 82.5(9)° and 79.8(9)° respectively,

Table 1 Important bond distances and bond angles of chloro-

bridged dimeric Ru(II) complexes [Ru₂(PPh₃)₂(µ-Cl)₂(tpy-C₆H₄-

CH=CH-Ar)₂]²⁺(1' and 3').

Fig. 1 Simulated and experimental isotopic distribution

1-4

pattern for the molecular ion peaks ([M-PF₆]⁺) of

obtained from HRMS (ESI+) (5-8 are in ESI).

Complex 1′

Complex 3′

Bond Distances (Å)

Ru1-Cl1

Ru1-P1

Ru1-N3

Ru1-N2

Furthermore, we intend to investigate the influence of σ-

donor ligand in the photophysical and electrochemical

properties for all the arylene-vinylene conjugated terpyridyl-

Ru(II) complexes. Thus, the complexes [Ph-C≡C-Ru(PPh₃)₂(tpy-

2.494(3)

2.284(3)

2.108(8)

1.947(9)

2.061(9)

1.294(19)

2.475(3)

2.294(3)

2.076(10)

1.956(8)

2.098(9)

1.298(17)

C₆H₄-CH=CH-Ar)][PF₆] (

coordinated chloride by phenylacetylide. The phenylacetylide

capped Ru(II) complexes ( ) were achieved by refluxing Ru(II)

complexes with phenylacetylene in presence of

5-8) were synthesized by substitution of

Ru1-N1

C22-C23

5-8

Bond Angles (°)

P1-Ru1-Cl1

N2-Ru1-Cl1

N2-Ru1-P1

(1-4)

97.65(10)

166.5(3)

84.5(3)

98.13(10)

89.2(2)

169.1(2)

92.8(3)

triethylamine in dry methanol in good yield (62-69%) after

purification through column chromatography using methanol

1

as mobile phase and neutral alumina as stationary phase. In H

95.3(3)

N2-Ru1-N1

N2-Ru1-N3

N1-Ru1-Cl1

N1-Ru1-P1

N1-Ru1-N3

N3-Ru1-Cl1

N3-Ru1-P1

N3-Ru1-Cl1

Cl1-Ru1-Cl1_i

P1-Ru1-Cl1_i

Ru1-Cl1-Ru1_i

Torsional Angles (°)

C7-C8-C16-C17

C9-C8-C16-C21

C20-C19-C22-C23

C22-C23-C24-C25

C22-C24-C33-C32

80.9(4)

79.5(4)

94.8(3)

86.5(2)

92.8(2)

160.4(4)

91.2(2)

79.1(3)

80.5(3)

88.5(2)

100.8(2)

91.6(2)

159.5(3)

90.1(2)

90.4(2)

NMR spectra, the protons adjacent to the pyridyl nitrogens

resonate at 8.87-8.88 ppm with an upfield shift by about 0.16

ppm compared to the complexes

1-4 with coordinated

chloride. The other aromatic protons resonate in the region of

6.88-7.91 ppm whereas the aromatic carbons appear in the

region of 119.9-158.1 ppm. In ³¹P{¹H } NMR spectra of complex

5

-

8

, the singlet at 28.5–28.1 ppm attributes the presence of

coordinated PPh₃, which is downfield shifted by about 7 ppm

compared to the coordinated PPh₃present in The

89.4(2)

104.3(3)

82.50(9)

179.35(10)

97.50(9)

99.0(3)

1-4.

79.86(9)

177.98(10)

100.15(9)

presence of counter anion is confirmed by ³¹P{¹H} NMR

showing multiplet at -143.5 ppm and IR spectra exhibiting

ῡ(PF₆) at 842 cm^-1. The formation of ruthenium(II) acetylide

complexes (5-8

) was confirmed from ¹³C{¹H} NMR spectra

23.62

13.65

1.32

30.18

33.52

7.33

-31.99

0.08

showing a signal at 126.6-126.9 ppm, attributed to Ru-C≡C

moiety. Moreover, the characteristic ῡ_C≡C(C≡C aꢀached to

Ru(II)) stretching frequency for all the phenylacetylide capped

Ru(II) complexes (5-8

) appears at 2063-2064 cm^-1. Finally, the

6.84

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favored due to the accessibility of externally added PPh₃

ligand, resulting coordinately saturated mononuclear distorted

2

Important bond distances and bond angles of

octahedral Ru(II) complexes (

1

and

3

). The P1-Ru1-P2 bond

mononuclear Ru(II) complexes [RuCl(PPh₃)₂(tpy-C₆H₄-CH=CH-

Ar)]⁺(1, 2 and 3).

angles are 174.14(4)°, 172.18(5)° for complex

1

and

3

respectively, revealing the trans orientation of the two P

atoms of the two PPh₃ligands. The two PPh₃ligands adopt a

nearly vertical position above the planar NNN terpyridyl ligand

as manifested by P1-Ru1-N1, P1-Ru1-N2 and P1-Ru1-N3 bond

angles which are in the range of 80.82(11)°-105.61(10)° and

Complex 1 Complex 2 Complex 3

Bond Distances (Å)

Ru1-Cl1

Ru1-P2

Ru1-P1

Ru1-N2

Ru1-N3

Ru1-N1

C22-C23

2.4902(13) 2.4382(16) 2.486(2)

2.4679(14) 2.4086(17) 2.463(2)

2.4621(14) 2.4118(17) 2.456(2)

87.04(13)°-92.17(13)° for complex

1 and 3 respectively. The

1.999(4)

2.085(4)

2.075(4)

1.457(8)

1.955(5)

2.094(5)

2.078(5)

1.437(8)

2.000(6)

2.056(7)

2.054(6)

1.427(13)

bond angles for P2-Ru1-N1, P2-Ru1-N2 and P2-Ru1-N3 are

observed in the similar range of 83.04(11)°-103.38(11)° and

89.12(13)°-93.89(13)° respectively for complex

P1-Ru1-Cl1 and P2-Ru1-Cl1 bond angles are 95.85(4)°,

86.46(5)° and 79.23(4)°, 87.53(5)° for complex and

1 and 3. The

Bond Angles (°)

P2-Ru1-Cl1

P1-Ru1-Cl1

P1-Ru1-P2

1

3

95.85(4)

79.23(4)

174.14(4)

86.46(5)

87.53(5)

172.18(5)

79.22(7)

96.87(7)

174.63(7)

respectively, demonstrating that Cl1 is almost orthogonal with

the P atoms (P1 and P2) of the two PPh₃ligands. Thus, the

N2-Ru1-Cl1

N2-Ru1-P2

N2-Ru1-P1

N2-Ru1-N3

N2-Ru1-N1

N3-Ru1-Cl1

N3-Ru1-P2

N3-Ru1-P1

N1-Ru1-Cl1

N1-Ru1-P2

N1-Ru1-P1

N1-Ru1-N3

Torsional Angles (°)

C7-C8-C16-C17

C9-C8-C16-C17

C20-C19-C22-C23

C22-C23-C24-C25

C23-C24-C33-C32

178.45(13) 179.60(13) 178.6(2)

solid state structure of complex

1 and 3 revealed that Ru(II)

83.04(11)

101.82(11) 92.17(13)

77.19(16)

80.45(17)

93.82(13)

82.09(18)

101.76(18)

77.1(3)

center is six coordinated to form a distorted octahedron built

by three ‘N’ atoms of terpyridine unit, one ‘Cl’ atom and two

trans-oriented ‘P’ donors of PPh₃. Moreover, the single crystal

78.84(19)

79.46(18)

80.3(3)

of complex

solution of complex

PPh₃. The molecular structure of the mononuclear Ru(II)

complex exhibited similar coordination environment around

the Ru(II) metal center as observed for the other mononuclear

Ru(II) complexes ( and ) (Fig. 2 and Table 2). However,

chloro-bridged dimeric crystal, [Ru₂(PPh₃)₂(µ-Cl)₂(tpy-C₆H₄-

CH=CH-C₆H₄-CH₃)₂]²⁺was not obtained for complex

in the

crystallization medium. The Ru1-P1 and Ru1-P2 bond length of

mononuclear Ru(II) complex are 2.4621(14) and 2.4621(14) Å

respectively which is nearly similar with the Ru1-P1 and Ru1-

P2 bond length of complex (2.456(2) and 2.463(2) Å

respectively). In contrast, the Ru1-P1 (2.4118(17) Å) and Ru1-

P2 (2.4086(17) Å) bond lengths in complex are relatively

shorter than the other mononuclear Ru(II) complexes ( and

). Thus, the relatively stronger Ru-P bond of complex

2

was also obtained by layering hexanes on DCM

101.46(11) 101.43(14) 101.67(17)

2

in the presence of externally added

72.07(10)

93.89(13)

71.49(17)

105.61(10) 92.19(13)

105.54(17)

2

100.88(12) 100.27(13) 100.87(18)

103.38(11) 89.12(13)

80.82(11) 87.04(13)

103.10(18)

81.36(18)

1

3

157.55(16) 158.24(18) 157.3(2)

2

-44.01

-46.85

-24.49

-17.72

-45.26

-46.35

-23.39

-18.66

-45.31

-45.05

38.34

-60.38

-2.63

1

3

2

suggesting the two chlorides are cis positioned. The PPh₃

ligand adopts a nearly orthogonal position above the planar

NNN terpyridyl ligand as manifested by P1-Ru1-N1, P1-Ru1-N2

and P1-Ru1-N3 bond angles are in the range of 89.4(2)° -

95.3(3)° (Table 1) respectively for dinuclear Ru(II) complex 1′

and 3′. The P1-Ru1-Cl1 bond angles are 97.6(10)° and 98.1(10)°

for complex 1′ and 3′ respectively, demonstrating that Cl1 is

positioned orthogonally to the P atom of PPh₃ligand. Thus, the

molecular structures of complex 1′ and 3′ revealed that both

the Ru(II) center is six coordinated to form a distorted-

octahedral geometry built by the three ‘N’ donor of terpyridyl

ligand, one ‘P’ donor of PPh₃, and two cis-chlorides. To

prevent the dissociation of coordinated PPh₃, ca. 1.5

equivalent of PPh₃was added externally into the DCM solution

of the respective Ru(II) complexes. Interestingly, the desired

monomeric Ru(II) complexes [Ru(PPh₃)₂Cl(tpy-C₆H₄-CH=CH-

1

3

2

disfavour the dissociation of PPh₃ligand and hinders

consequent dinuclear Ru(II) complex formation. The Ru1-Cl1

bond length of complex

1 and 3 are 2.49(13) and 2.48(16) Å

which are similar than that (2.49(3) and 2.47(3) Å) in the

respective dinuclear Ru(II) (1′ and 3′) complexes (Table 1 and

Table 2). However, the Ru1-Cl1 bond length of complex

2.43(16) Å which is relatively shorter than that of the other

mononuclear Ru(II) complexes ( and ). The molecular

structures of the Ru(II) complexes ( and ) and the

2 is

1

3

1,

2

3

corresponding chloro-bridged dimers (1′ and 3′) revealed the E

1

configuration of the vinylene linkage as also supported by H

NMR (vide-supra). Fig. 2 represents the ORTEP view of the

molecular structures of the mononuclear (1, 2 and 3) and

Ar)]⁺(

1 and 3) were crystallized by layering hexanes on PPh₃

dinuclear (1′ and 3′) Ru(II) complexes, while selected bond

angles and bond lengths are listed in Table 1 and Table 2.

added DCM solution of the respective Ru(II) complexes (Fig. 2).

During crystallization, the chloro-bridged dimerization was not

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Fig. 2 Molecular structure of [Ru₂(PPh₃)₂(µ-Cl)₂(L1)₂]²⁺(1'), [Ru(PPh₃)₂Cl(L1)]⁺(1), [Ru₂(PPh₃)₂(µ-Cl)₂(L3)₂]²⁺(3'), and [Ru(PPh₃)₂Cl(L3)]⁺

(3) and [Ru(PPh₃)₂Cl(L2)]⁺(2). Partial labelling and omission of Hydrogen atoms have been made for sake of clarity. The thermal

ellipsoids are drawn at 40% of probability.

the time correlated single photon counting (TCSPC) method.

The photophysical and lifetime data of all the arylene-vinylene

Photophysical properties

To realize the substitution effect on the aryl groups on

electronic properties of the arylene-vinylene conjugated

terpyridines, the absorption and emission spectra of L1-L4

were investigated both in solution and solid states. The

absorption and emission spectra of the ligands were measured

in CHCl₃with a concentration at about 1×10^-5M at ambient

temperature. All the ligands showed λ_maxcentered at 332-390

nm ascribing the π- π* transition of the conjugated molecular

backbone which is well agreement with the similar reported

Fig. 3 Absorption spectra of the Ru(II) complexes (a)

complex 1-4 (b) complex 5-8 in 1×10^-5M CHCl₃solution at

ambient temperature.

ligands (Fig. S63, ESI).^11eIn photoluminescence spectra of L1-

L4, a gradual bathochromic shift was observed exhibiting blue

to green fluorescence while going from L1 to L4 (Fig. S64, ESI).

In case of L1-L3, the compounds showed blue fluorescence

with emission maxima at 412, 417 and 437 nm respectively

whereas L4 exhibited green fluorescence with emission

maxima at 498 nm which is supported by similar literature

reported ligands.^11eThe fluorescence quantum yields (Φ) of all

the ligands were measured in CHCl₃using quinine sulfate (Φ =

0.54) in 0.1 M H₂SO₄solution as a reference at ambient

temperature.¹²The PL quantum yields of compounds L1-L4 are

in the range of 0.17-0.36, showing a gradual increase with

extending π-delocalization. The fluorescence lifetime of all the

complexes were found to be in the range of 1.33-2.88 ns by

conjugated terpyridines are summarized in Table S2.

The Ru(II) incorporated arylene-vinylene conjugated

terpyridyl complexes (1-4) exhibited ligand based low energy

absorption band showing λ_maxin the region 364-390 nm which

can be ascribed as π to π* transition while the high energy

band (314-317 nm) can be ascribed as ICT transition.

Interestingly, a new absorption band in the visible region (496-

500 nm) is appeared which originates from dπ(Ru)-π* (arylene-

vinylene unit) transition coined as metal to ligand charge

transfer transition (MLCT).¹³The Ru(II)-acetylide complexes (5-

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8) showed the similar properties in the absorption spectra. In oxidation of anthracenyl moiety. The corresponding cathodic

this case, the low energy and high energy absorption band wave was appeared at -1.33 V. The electrochemical data of the

centered at 368-400 nm and 316-317 nm can be ascribed as π Ru(II) complexes (1-4) were also investigated in acetonitrile to

to π* and ICT transition respectively (Fig. 3). Moreover, the gain an insight into the oxidation or reduction process in wider

MLCT band is red shifted to 514-517 nm which is due to the positive and negative potential window. No change in anodic

incorporation of the phenylacetylide moiety to complex 5-8 or cathodic waves was observed for the one electron oxidation

offer extended π-conjugation (Table 3) due to the filled/filled of Ru^II/Ru^IIIdemonstrating the solvent independent nature of

interaction between acetylide π orbitals and metal dπ the electrochemical process (Fig. S70 and Table S4). However,

an irreversible oxidation waves at high positive potential were

Table 3 Absorption spectral data of the arylene-vinylene

conjugated terpyridyl Ru(II) at ambient temparature

observed at + 1.65, +1.52, +1.68 and +1.54 V for complex 1-4

respectively which is presumably due to oxidation of the

terpyridyl group. The corresponding irreversible reduction

Compound Solution State

Solid state

waves of 1-4 were occurred at -1.38, -1.51, - 1.53, -1.55 V

respectively. For complex 1-4, The anodic waves originating

from the oxidation of the terpyridyl groups, in the high

positive region, were not observed in DCM as a result of the

restriction of the potential window for DCM (+1.5 to -1.5 V).

Similar electrochemical behavior for the naphthyl and

a

b

λ_max

-1

4

[ ε (M .cm ) × 10 ]

L1

L2

L3

L4

1

333(4.1), 288(3.2)

346, 284

354, 285

357, 286

408, 263

362, 506

366, 511

362, 513

394, 538

334(4.8), 285(3.1)

341(5.6), 284(5.0)

anthracenyl groups (as in DCM) in complex

3 and 4 were

390(1.0),258(9.0)

observed in acetonitrile also as tabulated in Table S4 (ESI).

316(0.49), 364(4.5), 496(1.1)

317(0.43), 368(3.7), 497(1.1)

315(0.32), 366(2.4), 498(0.8)

314(0.29), 390(1.1), 500(0.66)

To investigate the change in electronic property of the

phenylacetylide-capped arylene-vinylene conjugated terpyridyl

Ru(II) complexes (5-8), cyclic voltammetry and differential

pulse voltammetry were also carried out in DCM, using the

similar set of experimental condition (Fig. 4). DCM has been

chosen as solvent for the electrochemical measurements as

these complexes are poorly soluble in CH₃CN. As observed in

2

3

4

5

6

7

8

316(0.43), 376(3.1), 514(1.0)

317(0.46), 373(2.7), 516(0.8)

316(0.40), 368(3.3), 516(1.1)

317(0.36), 391(1.4), 517(0.8)

383, 516

380, 519

384, 530

396, 542

1-4, phenylacetylide-capped Ru(II) complexes (5-8) showed

similar reversible one electron oxidation processes with

relatively lower E_1/2values of 0.67-0.79 V (vs Ag/AgCl)

presumably due to substitution of the chloride ligand

^aAbsorption data in 1×10^-5M CHCl₃; ε =Absorption

coefficient.; ^bAbsorption data as thin film on quartz

substrate.

coordinated to Ru(II) centers by

a stronger σ-donor

phenylacetylide moiety. Consequently, the oxidation of the

orbitals.^2lThe Ru(II) complexes were found to be nonemissive

Ru(II) center is easier for the complexes 5-8. Similar to complex

in nature.

3

and 4, the anodic waves in the high positive region of

Electrochemical studies

To understand the electronic and electrochemical properties

of the arylene-vinylene conjugated terpyridyl Ru(II) complexes

Table 4. Electrochemical data for Ru(II) complexes (1-8) in

DCM.

Complex

anodic

^aE_pa(V)

cathodic

^aE_pc(V)

-1.39

(

1-4), cyclic voltammetry (CV) and differential pulse

voltammetry (DPV) analysis were conducted at scan rate of

n

^bE_1/2(V)

0.93(84)^c

0.93(70^c

0.94(84)^c

100 mVs^-1using Bu₄NPF₆(0.1 M) as supporting electrolyte, Pt

1

2

3

4

5

6

7

8

-

disc working electrode and Ag/AgCl as reference electrode in

DCM. The anodic cyclic voltammograms (CVs) and differential

pulse voltammograms (DPVs) of the ruthenium(II) complexes

-

-1.33

1.46

-1.38

1.44, 1.18 0.94(60)^c

-1.33, -1.45

-1.42

-

0.67(81)^c

0.69(65)^c

0.70(75)^c

(

1-4) are depicted in Fig. 4. Complex 1-4 exhibited reversible

oxidation wave in the potential region from 0.93-0.94 V due to

one electron oxidation (Ru^II/Ru^III) process. The peak-to-peak

potential difference of each Ru^II/Ru^IIIredox couple for all the

complexes are around 60-84 mV which is in good agreement

with one electron Nernstian process. Interestingly, at high

-

-1.42

1.18

-1.47

1.23, 1.08 0.79(76)^c

-1.30, -1.43

Condition: Pt-disc working electrode, Ag/AgCl reference

electrode, Pt wire counter electrode, 0.1 M TBAPF₆in

positive potential, complex

3 showed an irreversible oxidation

DCM, scan rate 100 mV s^-1at 25 C. irreversible redox

°

a

peak (E_pa) at +1.46 V which is likely associated with the

oxidation of naphthalene unit attributing to the formation of

the radical cation, [naphthalene]^+•and the corresponding

irreversible reduction peak (E_Pc) was appeared at -1.38 V.

waves. ^breversible redox waves. corresponding E_pa-E_pc

values (in mV) in parenthesis.

c

Similar electrochemical behavior was observed for

4 with an

additional irreversible oxidation wave at +1.18 V due to

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The highest occupied molecular orbitals (HOMOs) of the

complexes exhibit an antibonding interactions between

1-3

the ruthenium d-orbitals and one of the p-orbitals of chloride

ligand in one side, and one of the heterocyclic nitrogen atoms

on the other side (Fig. S73). The contribution of the d-orbital

(23.7-10.8%) of ruthenium in HOMO decreases from

1 to 3,

resulting in slight increase in the energy of the corresponding

HOMO. On the other hand, the energy of the lowest

unoccupied molecular orbitals (LUMOs) is found to be

unperturbed for the complexes 1-3, as shown in Fig. 5 and Fig.

S73. Moreover, the contribution of ruthenium d-orbital to

LUMO remains almost same (4.8-5.0%) in these three

complexes (Table S5, ESI). The gradual increase in the energy

of HOMOs and the unperturbed LUMOs in complexes

1-3

result in a net decrease in the energy gap between the

respective HOMO and LUMO (5.49, 5.41 and 5.38

respectively). In complex

4, The HOMO is predominantly

Fig. 4 Cyclic voltammograms (CV) and differential pulse

voltammograms (DPV) of Ru(II) complexes (1-8) in DCM at

a scan rate of 100 mV s^-1. Potentials are given relative to

the Ag/AgCl used as reference electrode.

complex

7 and 8 were also appeared with significant lowering

Fig. 5 Energy level diagram of the frontier molecular

orbitals of the Ru(II) complexes (1- 8) estimated by DFT

levels.

in E_pavalues as tabulated in Table 4.

The electrochemical behavior of the Ru(II) centre is tuned

by varying the ligand to phenylacetylide from chloride in the

synthesized arylene-vinylene conjugated terpyridyl Ru(II)

complexes. These observations also provide good evidence

that π-conjugation in the ligands and coordination

environment of metal components employs an impact on the

oxidation and consequent delocalization along the organic

backbone.

localized on the arylene-vinylne group with minor contribution

from Ru(II)-metal center. This is accompanied by a further

increase of the energy of HOMO, thereby decreasing the

HOMO-LUMO energy gap to a much larger extent (Fig. 5). The

nature of LUMO in complex

observed in . However, in complex

(0.67 eV lower in energy than the HOMO), is similar in bonding

character to that of the HOMOs of complexes , with

ruthenium d-orbital character contribution amounting to

57.9%. In the cyclic voltammogram studies of complex (Fig.

4, however, remains similar as

1-3

4, the HOMO-1 orbital

Theoretical studies

1-3

To gain an insight on the geometrical and electronic structural

properties, all the complexes (1-8) were subjected to geometry

optimization by Density Functional Theory (DFT) with CAM-

B3LYP functional,¹⁴where all the atoms were treated with

def2-TZVP basis set.¹⁵To incorporate the effect of solvation,

polarization continuum model (PCM) was employed with

dichloromethane (DCM) as the solvent.¹⁶The normal modes of

vibration of the complexes were determined by carrying out

Hessian calculations at the respective optimized geometries of

the complexes. Thermodynamic stability of all the eight

complexes was confirmed from the absence of imaginary

frequencies in the normal modes of vibration. All geometry

optimizations were performed using Gaussian 09 software.¹⁷

Orbital composition analysis¹⁸of the resulting wave functions

of the complexes was carried out by the Multiwfn program.¹⁹

1-3

4), the redox waves corresponding to Ru(II)/Ru(III) couple

appears nearly at same position which can be illustrated by the

similar HOMO energy levels (-7.32, -7.23 and -7.22

respectively) as evident from the DFT study. In complexes 5-8,

the chlorides were replaced by σ-donor phenylacetylide

moiety and interestingly the contribution of metal d-orbital in

the respective HOMOs increased significantly (37.4-37.9%) in

comparison to those of

1-4. As expected, the HOMOs in

complexes 5-8 are found to be composed of ruthenium d-

orbitals undergoing strong bonding overlap with the adjacent

nitrogen atoms and the filled/filled interaction with the π-

orbitals of phenylacetylide (Fig. 6).^2lSuch increase in extended

conjugation due to the presence of phenylacetylide termini

leads to a reduction of the HOMO-LUMO gap in

5-8. In

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complex

8, the spacing between HOMO–1 and HOMO is of inorganic-organic hybrid Ru(II) complexes are underway in

significantly smaller (0.09 eV) which may induce transition our laboratory for developing NIR absorbing metal-organic

from HOMO–1 to LUMO in combination with HOMO to LUMO. electrophores.

These can also be ascribed by the appearance of multiple

Experimental

Materials and methods

All moisture sensitive reactions and manipulations were

carried out under an atmosphere of pre-purified Ar or N₂by

using standard Schlenk techniques. The glasswares were oven-

o

dried (at 180 C) and cooled under vacuum. Tetrahydrofuran

and toluene were dried over Na/benzophenone whereas dry

DCM, methanol and CCl₄were obtained by distillation over

CaH₂. Unless otherwise mentioned all chemicals were

analytical grade, obtained from Aldrich, and used without

further purification. Triphenylphosphine and aryldehydes were

purchased from Spectrochem. Metal precursor (RuCl₃.xH₂O)

was acquired from Arora Matthey. Silica gel (60–120 mesh)

and neutral alumina used for column chromatography, was

purchased from Merck. Eluting systems for column

chromatography purifications were determined by thin layer

chromatography (TLC) analysis. TLC plates were visualized

under UV light (254 nm/365nm). Solvents were evaporated

under reduced pressure using

a

rotary evaporator.

Ru(PPh₃)₃Cl₂were synthesized by the procedures described in

literature methods.

¹H (600 MHz and 400 MHz), ¹³C{¹H} (150 MHz and 100

MHz) and ³¹P {¹H} (162 MHz) spectra were obtained from

Bruker Lambda spectrometer using CDCl₃unless otherwise

mentioned. Spectra were internally referenced to residual

solvent peaks (δ = 7.26 ppm for proton and δ = 77.23 for

carbon (middle peak) in CDCl₃or an externally capillary of 85%

H₃PO₄for ³¹P {¹H} NMR. All coupling constants (J) are given in

Hz. The HRMS mass spectra were recorded in ESI⁺mode (70

eV) in Waters (Model: Xevo-G2QTOF). The absorption and

fluorescence spectra were collected using a Shimadzu (Model

UV-2450) spectrophotometer and a Hitachi (Model F-7000)

spectrofluorimeter respectively. The time-resolved emission

decays were recorded using a time correlated single photon

counting (TCSPC) picoseconds spectrophotometer (Model IBH,

UK). FTIR spectroscopy was recorded in Spectrum-BX (Perkin

Elmer). Single-Crystal data was collected in low temperature

mode using Bruker Apex-II instrument. Cyclic voltammetric

studies were performed on a BASi Epsilon electrochemical

Fig. 6 Frontier molecular orbitals of the Ru(II) complexes

) estimated by DFT calculations using CAM-B3LYP

functional and def2-TZVP basis set.

(5-8

redox processes apart from the first Ru(II)/Ru(III) redox wave.

Conclusions

In this work, a series of arylene-vinylene conjugated terpyridyl

ruthenium(II) complexes bearing chloride and σ-donor

phenylacetylide ligands have been developed by varying the

electronic nature of the arylene group. The Ru(II) complexes (

1

and 3) crystallize as chloro-bridged dimers due to the facile

dissociation of one PPh₃ligand whereas the desired

monomeric single crystals were achieved by addition of PPh₃

externally. The ruthenium(II) metal center is in distorted

octahedral environment in its monomeric and in the

corresponding chloro-bridged dimeric form. Moreover, the

structural investigation shows that the arylene-vinylene group

is in trans conformation. The electrochemical study revealed

that one electron oxidation for Ru^II/Ru^IIIprocess occurred in

the potential region at 0.93-0.94 V and 0.67-0.79 V for

complex 1-4 and 5-8 respectively. The Ru(II) complexes bearing

phenylacetylide termini (5-8) showed significant lowering in

E_1/2values of Ru^II/Ru^IIIprocess due to the substitution of the

workstation in acetonitrile with 0.1

M

tetra-n-

butylammoniumhexafluorophosphate (TBAPF₆)

as the

supporting electrolyte. The working electrode was a BASi Pt

disc electrode, the reference electrode was Ag/AgCl and the

auxiliary electrode was a Pt wire. The ferrocene/ferrocenium

couple occurs at E_1/2=+0.51 (70) V versus Ag/AgCl under the

same experimental conditions. The DFT study of all the Ru(II)

complexes were analyzed using CAM-B3LYP/ DEF2-TZVP basis

set in conjunction of polarization continium model (PCM)

together with dichloromethane as solvent.

chloride ligand (complex 1-4) by a stronger σ-donor

phenylacetylide termini, which was also well supported by the

he DFT studies revealing the difference in E_gbetween the

series of compounds 1-4 and 5-8. Functionalization of this class

X-ray data collections and refinement

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Single-crystal X-ray structural study was performed on a 132.9, 134.9, 137.1, 136.6, 139.3, 145.2, 155.4, 157.2, 158.1;

Bruker-APEX-II CCD X-ray diffractometer equipped with an ³¹P{¹H} (CDCl₃, 162 MHz): 20.02, -143.54; HRMS (ESI⁺):

Oxford Instruments low-temperature attachment. Data were C₆₅H₅₁N₃ClP₃F₆Ru, Calculated value 1072.2290 ([M-PF₆]⁺),

collected at 100(2) K for complex

1

,

1′

,

2

,

3′ whereas complex

3

experimental 1072.2383 ([M-PF₆]⁺); FTIR (KBr, ꢀꢁ, cm^-1): 846

-

data was collected at 293(2) K using graphite-monochromated (PF₆); λ_max(ε): 364 nm (ɛ = 4.5 × 10⁴Lmol^-1cm^-1), 496 nm (ɛ =

Mo Kα radiation (λα = 0.71073 Å). The frames were indexed, 1.1 × 10⁴Lmol^-1cm^-1).

integrated, and scaled using the SMART and SAINT software Synthesis of 2: Complex

package,²⁰and the data were corrected for absorption using procedure as that for complex

the SADABS program.²¹The single crystals were grown on 8 mmol), and Ru(PPh₃)₃Cl₂(90 mg, 0.094 mmol) and NaPF₆(29

2

was prepared using a similar

1, using L2 (40 mg, 0.094

mm O.D. glass tube. In complex 1, two independent molecules mg, 0.188 mmol). The pure product was isolated as brown red

and one half of dichloromethane molecules were located in crystalline solid. Yield: 102 mg (89%); ¹H NMR (CDCl₃, 600

the asymmetric unit with negligible differences in their MHz): δ 2.43 (s, 3H, Me), 7.08-7.06 (m, 16H), 7.21-7.18 (m,

metrical parameters. For complex

3, one independent 18H), 7.50-7.43 (m, 4H), 7.69-7.65 (m, 2H), 7.73-7.70 (m, 2H,

molecule and one half of dichloromethane molecule were Py), 7.76-7.75 (m, 4H, Py), 7.94-7.93 (m, 2H, Py), 9.04-9.03 (m,

located in the asymmetric unit. Two independent molecules 2H, Py); ¹³C{¹H} NMR (150 MHz, CDCl₃) δ ¹³C{¹H} NMR (150

and two one half of dichloromethane molecules were located MHz, CDCl₃) δ 29.9, 115.4, 115.7, 115.8, 120.2, 122.8, 125.9,

in the asymmetric unit of complex

in their metrical parameters. CCDC1828213-1828217 contain 130.2, 130.1, 133.3, 134.6, 136.8, 139.6, 145.5, 155.5, 157.4,

the supplementary crystallographic data for the complexes

158.3; ³¹P{¹H} (CDCl₃, 162 MHz): 20.02, -149.54; HRMS (ESI⁺):

’, and

2 with negligible differences 126.4, 127.6, 127.8, 128.3, 128.4, 129.5, 129.6, 129.9, 130.0,

1

,

2

,

3

,

1

3

’. These data can be obtained free of charge from C₆₆H₅₃N₃ClP₃F₆Ru, Calculated value 1086.2447 ([M-PF₆]⁺),

The Cambridge Crystallographic Data Centre via experimental 1086.2477 ([M-PF₆]⁺); FTIR (KBr, ꢀꢁ, cm^-1): 845

www.ccdc.cam.ac.uk/data_request/cif. The structures were (PF₆); λ_max(ε): 368 nm (ɛ = 3.7 × 10⁴M^-1cm^-1), 497 nm (ɛ = 1.1 ×

-

solved by SHELXT²²and refined with SHELXL²³using Olex2 10⁴M^-1cm^-1).

program.²⁴The molecular structure was generated by using Synthesis of 3: Complex

3

was prepared using a similar

ORTEP-3 for Windows Version 2.02.37.²⁵The hydrogen atoms procedure as that for complex

1, using L3 (74 mg, 0.160

were included in geometrically calculated positions in the final mmol), and Ru(PPh₃)₃Cl₂(153 mg, 0.160 mmol) and NaPF₆(51

stages of the refinement and were refined according to the mg, 0.320 mmol). The pure product was isolated as brown red

typical riding model. All non-hydrogen atoms (except C22 and crystalline solid. Yield: 180 mg (86%); ¹H NMR (CDCl₃, 600

C30 in complex

parameters.

3

) were refined with anisotropic thermal MHz): δ 7.09-7.06 (m, 16H), 7.21-7.19 (m, 18H), 7.48-7.46 (m,

1H), 7.56-7.52 (m, 2H), 7.62-7.60 (m, 1H), 7.74-7.70 (m, 2H),

7.82-7.81 (m, 3H), 7.86-7.84 (m, 3H), 7.91-7.89 (m, 1H), 7.97-

Synthesis and characterization

7.96 (m, 2H), 8.09-8.06 (d, 1H, J = 18 Hz), 8.32-8.30 (d, 2H, J =

Compounds L1-

L4 have been synthesized following the 12 Hz), 9.04-9.03 (m, 2H, Py); ¹³C{¹H} NMR (CDCl₃, 150 MHz): δ

literature procedure (ESI).^11a,e

120.1, 122.7, 123.8, 125.7, 125.9, 126.2, 126.4, 127.5, 127.5,

128.0, 128.2, 128.2, 128.3, 128.5, 128.7, 129.7, 129.8, 129.9,

130.1, 130.6, 132.9, 132.9, 132.9, 133.8, 134.7, 136.6, 157.2,

155.3, 158.1; ³¹P{¹H} (CDCl₃, 162 MHz): 20.02, -143.54; HRMS

(ESI⁺): C₆₉H₅₃N₃ClP₃F₆Ru, Calculated value 1122.2447 ([M-

PF₆]⁺), experimental 1122.2493 ([M-PF₆]⁺); FTIR (KBr, ꢀꢁ, cm^-1):

Synthetic procedure for complex 1-4

Synthesis of 1: In an oven-dried 100 mL Schlenk flask that had

been thoroughly purged with Ar was charged with 12 mL of

degassed methanol. L1 (40 mg, 0.097 mmol), and Ru(PPh₃)₃Cl₂

(92 mg, 0.097 mmol) were added to it. The reaction mixture

was heated to reflux for 24 h under Ar atmosphere. Then the

mixture was allowed to cool to room temperature and diluted

with distilled methanol (5 mL). The mixture was then filtered

through a pad of celite (~3 cm tall × 4 cm dia). The celite pad

was rinsed with distilled methanol until the eluent became

colorless. Solid NaPF₆(29 mg, 0.194 mmol) was added to the

combined filtrates and the solution was kept in freeze for

overnight. During this time wine-red color precipitate emerged

which was collected, washed with copious amounts of diethyl

ether and dried under high vacuum to afford the desired

-

841 (PF₆); λ_max(ε): 366 nm (ɛ = 2.4 × 10⁴M^-1cm^-1), 498 nm (ɛ =

0.8 × 10⁴M^-1cm^-1).

Synthesis of 4: Complex

4

was prepared using a similar

, using L4 (40 mg, 0.078

procedure as that for complex

1

mmol), and Ru(PPh₃)₃Cl₂(75 mg, 0.078 mmol) and NaPF₆(24

1

mg, 0.156 mmol). Yield: 104 mg (79%); H NMR (CDCl₃, 600

MHz): δ 7.10-7.07 (m, 16H), 7.22-7.20 (m, 18H), 7.52-7.50 (m,

4H), 7.75-7.71 (m, 4H), 8.00-7.86 (m, 4H), 8.14-8.04 (m, 4H),

8.45-8.40 (m, 3H), 9.05-9.04 (m, 2H, Py); ¹³C{¹H} NMR (CDCl₃,

150 MHz): δ 120.1, 122.7, 125.28, 125.71, 126.0, 126.2, 126.8,

127.3, 127.5, 128.1, 128.2, 128.3, 128.7, 129.8, 129.9, 130.0,

131.5, 132.3,. 132.9, 134.1, 135.4, 136.3, 136.7, 139.1, 145.1,

155.4, 157.3, 158.1; ³¹P{¹H} (CDCl₃, 162 MHz): 20.02, -143.54;

HRMS (ESI⁺): C₇₉H₅₅N₃ClP₃F₆Ru, Calculated value 1172.2603

([M-PF₆]⁺), experimental 1172.2686 ([M-PF₆]⁺); FTIR (KBr,

1

product as a brown crystalline power. Yield: 95 mg (84%); H

NMR (CDCl₃, 600 MHz): δ 7.08-7.06 (m, 14H), 7.21-7.19 (m,

20H), 7.32-7.29 (m, 3H), 7.60-7.59 (m, 2H), 7.67 (s, 2H, Py),

7.73-7.71 (m, 2H, Py), 7.77 (s, 2H, Py), 7.95-7.94 (m, 2H, Py),

9.04-9.03 (m, 2H, Py); ¹³C{¹H} NMR (CDCl₃, 150 MHz): δ 120.0,

122.6, 126.2, 126.8, 126.9, 127.4, 127.5, 127.8, 128.1, 128.2,

128.3, 128.5, 128.6, 128.8, 129.8, 129.9, 130.1, 130.5, 132.1,

-

ꢀꢁ, cm^-1): 841 (PF₆); λ_max(ε): 390 nm (ɛ = 1.1 × 10⁴M^-1cm^-1), 500

nm (ɛ = 0.66 × 10⁴M^-1cm^-1).

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Synthetic procedure for complex 5-8

155.1, 156.9, 158.1; ³¹P{¹H} (CDCl₃, 162 MHz): 28.02, -143.54;

HRMS (ESI⁺): C₇₇H₅₈N₃P₃F₆Ru, Calculated value 1188.3148 ([M-

PF₆]⁺), experimental 1188.3170 ([M-PF₆]⁺); FTIR (KBr, ꢀꢁ, cm^-1):

Synthesis of 5: In an oven-dried 100 mL Schlenk flask that had

been thoroughly purged with Ar was charged complex

1 (100

-

2066 (C≡C), 837 (PF₆); λ_max(ε): 368 nm (ɛ = 3.3 × 10⁴M^-1cm^-1),

mg, 0.082 mmol), phenylacetylene (21 mg, 0.205 mmol), 3 mL

of triethylamine and 12 mL of degassed methanol. The

reaction mixture was heated to reflux for 36 h. The solvent

was evaporated to a minimum volume after cooling to room

temperature. Wine red precipitate was obtained after addition

of hexane to the residue. The precipitate was filtered and

washed with hexane (10 mL) and ether (2 × 10 mL) and then

dried under vacuum to obtain solid product. The solid residue

was further purified by column chromatography (ethyl

acetate: hexane, 4:1) on neutral alumina to achieve

analytically pure wine red solid product. Yield: 81 mg (63%); ¹H

NMR (CDCl₃, 600 MHz): δ 6.88-6.82 (m, 2H), 7.08-7.06 (m,

14H), 7.21-7.17 (m, 10H), 7.32-7.28 (m, 4H), 7.43-7.40 (m,

12H), 7.81-7.76 (m, 6H), 7.93-7.91 (d, 2H, J = 12 Hz), 8.88-8.87

(m, 2H, Py); ¹³C{¹H} NMR (150 MHz, CDCl3): δ 119.9, 122.9,

124.5, 126.1, 126.9, 127.7, 127.8, 128.0, 128.2, 128.3, 128.4,

128.5, 128.7, 129.0, 129.7, 129.9, 130.2, 130.6, 130.8, 130.9,

131.0, 132.3, 135.6, 136.4, 137.3, 139.4, 146.5, 155.1, 156.9,

158.1; ³¹P{¹H} (CDCl₃, 162 MHz): 28.02, -143.54; HRMS (ESI⁺):

C₇₃H₅₆N₃P₃F₆Ru, Calculated value 1138.2993 ([M-PF₆]⁺),

experimental 1138.2987 ([M-PF₆]⁺); FTIR (KBr, ꢀꢁ, cm^-1): 2065

516 nm (ɛ = 0.8 × 10⁴M^-1cm^-1).

Synthesis of 8: Complex

8

was prepared using a similar

(60 mg, 0.110 mmol),

procedure as that for 5 using complex

4

phenylacetylene (23 mg, 0.225 mmol), triethylamine (1 mL)

and 7 ml of degassed methanol. The pure product was isolated

1

as wine red solid. Yield: 96 mg (66%).; H NMR (CDCl₃, 600

MHz): δ 6.87-6.89 (m, 2H), 7.06-7.08 (m, 14H), 7.17-7.2 (m,

10H), 7.31-7.28 (m, 4H), 7.40-7.43 (m, 14 H), 7.58-7.64 (m, 4H),

7.76- 7.81 (m, 6H), 7.91-7.93 (m, 2H), 8.87-8.88 (m, 2H);

¹³C{¹H} NMR (CDCl₃, 150 MHz): δ 119.9, 122.9, 124.5, 125.2,

125.5, 125.9, 126.1, 126.2, 126.9, 127.5, 127.9, 128.1, 128.4,

128.5, 128.9, 129.8, 129.9, 130.2, 130.7, 130.8, 130.9, 131.1,

131.7, 131.7, 132.2, 132.5, 132.6, 133.1, 134.4, 136.1, 136.4,

136.6, 139.3, 146.4, 155.1, 156.9, 158.2.; ³¹P{¹H} (CDCl₃, 162

MHz): 28.02, -143.54; HRMS (ESI⁺): C₈₁H₆₀N₃P₃F₆Ru, Calculated

value 1238.3304 ([M-PF₆]⁺), experimental 1238.3377 ([M-

-

PF₆]⁺); FTIR (KBr, ꢀꢁ, cm^-1): 2064 (C≡C), 840 (PF₆); λ_max(ε): 391

nm (ɛ = 1.4 × 10⁴M^-1cm^-1), 517 nm (ɛ = 0.8 × 10⁴M^-1cm^-1).

Acknowledgements

-

(C≡C), 845 (PF₆); λ_max(ε): 376 nm (ɛ = 3.1 × 10⁴M^-1cm^-1), 514

nm (ɛ = 1.0 × 10⁴M^-1cm^-1).

Authors acknowledge the support from the DST-SERB, India

through Fast Track scheme (SB/FT/CS-010/2012). SKP thanks

IIT Kharagpur for funding the purchase of the electrochemical

workstation through Competitive Research Infrastructure Seed

Grant (SGIRG, IIT/SRIC/CHY/PBR/2014-15/44). AS and SRC

acknowledge IIT KGP for doctoral fellowship.

Synthesis of 6: Complex

6

was prepared using a similar

(100 mg, 0.081 mmol),

procedure as that for 5 using complex

2

phenylacetylene (20 mg, 0.20 mmol), triethylamine (3.0 mL)

and 16 mL of degassed methanol. The pure product was

isolated as wine red solid. Yield: 67 mg, (62%) ; ¹H NMR (CDCl₃,

600 MHz): δ 2.39 (s, methyl 3H), 6.88-6.86 (m, 2H), 7.08-7.06

(m, 14H), 7.25-7.17 (m, 10H), 7.29-7.27 (m, 4H), 7.43-7.40 (m,

12H), 7.49-7.48 (m, 2H), 7.76-7.75 (m, 2H), 7.80-7.79 (m, 2H),

Conflicts of interest

7.94-7.91 (m, 2H), 8.87-8.86 (m, 2H, Py) ; ¹³C{¹H} NMR (CDCl₃, The authors declare no conflicts of interest.

150 MHz): δ 29.9, 119.9, 122.9, 124.5, 126.6, 127.7, 127.9,

128.4, 128.5, 128.6, 128.7, 129.0, 129.8, 130.2, 130.6, 130.8,

130.9, 131.1, 131.7, 132.3, 133.1, 134.5, 135.3, 136.4, 138.2, References

138.9, 139.6, 146.5, 155.1, 156.9, 158.2.; ³¹P{¹H} (CDCl₃, 162

1

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value 1152.3134 ([M-PF₆]⁺), experimental 1152.3149 ([M-

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nm (ɛ = 2.7 × 10⁴M^-1cm^-1), 516 nm (ɛ = 0.8 × 10⁴M^-1cm^-1).

Synthesis of 7: Complex

7

was prepared using a similar

(100 mg, 0.078 mmol),

procedure as that for 5 using complex

3

phenylacetylene (20 mg, 0.197 mmol), triethylamine (3 mL)

and 16 ml of degassed methanol. The pure product was

1

isolated as wine red solid. Yield: 74 mg (69%).; H NMR (CDCl₃,

600 MHz): δ 6.89-6.87 (m, 2H), 7.08-7.06 (m, 14H), 7.22-7.17

(m, 10H), 7.29-7.27 (m, 4H), 7.43-7.40 (m, 12H), 7.64-7.52 (m,

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TOC

A series of arylene-vinylene π-conjugated terpyridyl ruthenium(II) complexes have been synthesized and

characterized varying the aryl group and the ancillary ligands to modulate their redox and photophysical

properties.

J. Name., 2013, 00, 1-3 | 13

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Synthesis, structure, and photophysical and electrochemical properties of Ru(ii) complexes of arylene-vinylene terpyridyl conjugates

DOI: 10.1039/c8dt00881g

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