Scientific paper
Syntheses, Characterization, and Properties of Ru(II) Complexes Based on n-conjugated Terpyridine Ligand with Tetrathiafulvalene Moiety
Jie Qin,1'2 * Liang Hu,2 Na Lei,1 Yan-Fei Liu,1 Ke-Ke Zhang1
and Jing-Lin Zuo2
1 School of Life Sciences, Shandong University of Technology, Zibo, China
2 State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering,
Nanjing University, Nanjing, China
* Corresponding author: E-mail: qinjietutu@ 163.com
Received: 22-03-2014
Abstract
Two ruthenium(II) complexes [Ru(TTF-terpy)(terpy)][PF6]2 (terpy = 2,2 :6 ,2 -terpyridine) (1) and [Ru(TTF-terpy)2][PF6]2 (2) were synthesized by reactions of Ru(terpy)(dmso)2Cl2 or cis-Ru(dmso)4Cl2 with 4 -tetrathiafulvalene-2,2 :6 ,2 -terpyri-dine (TTF-terpy), respectively. The crystal structure of 1 has been determined by X-ray crystallography. In the crystal of complex 1, molecules are seized together into 1D chains via n—n stacking interactions. The electrochemical and spectroscopic properties of these compounds have been studied. The results show that these Ru(II) complexes show stepwise redox processes in solution, and are promising building blocks for the construction of multi-functional materials.
Keywords: Tetrathiafulvalene; Terpyridine ligand; Redox chemistry; Spectroscopic electrochemistry
1. Introduction
During the past decades, the field of multifunctional materials with molecule-based solids has gaining great interest. In particular, materials based on electrical conductivity and magnetic or optical interactions are currently the subject of intense investigation.1 Recently, in order to obtain multi-functional molecular materials, much attention has been devoted to association of the electrochemi-cally active tetrathiafulvalene (TTF) core with optical or magnetic properties of the metal ions bridged by various functional groups.2-5 To date, many TTF substituted derivatives have been reported, which might enable electron transfer and communication between the localized spins (d electrons) and the mobile n electrons.6-8 For further enhancing the interaction of this n-d system, it is important to shorten the distance between the metal ions and TTF units by designing new n-conjugated ligands.
2,2':6',2'-terpyridine (terpy) is a planar tridentate li-gand with powerful binding abilities toward transition-metal ions, and it usually acts as an electronic acceptor.9 El-Ghayoury and Salle et al. have successfully prepared
the TTF-based terpyridine ligand, 4-tetrathiafulvalene-2,2':6,2'-terpyridine (TTF-terpy) for the first time in 2013.10 For TTF-terpy, the TTF unit is directly connected to the terpyridine which significantly decreases the distance between the metal ion and TTF units. Later, we have developed a more simple and efficient synthetic route for the incorporation of TTF into terpyridine, and firstly reported the series of their Fe(II) complexes.11
Ru(II) complexes have been most intensely studied among the transition-metal complexes.12 For example, the C2-symmetric diphosphine/diamine based Ru(II) complexes can be used as excellent catalyst precursors in asymmetric transfer hydrogenation of acetophenone.13 Tris(2,2'-bipyridyl) Ru(II) complex show high photoluminescence and electroluminescence efficiency in light-emitting devices.14 Ru(II) polypyridyl complex with a terpyridine/phenylimidazo[4,5-f]-phenanthroline hybrid was investigated as an effective turn on luminescence sensor for H2PO4".15 Introduction of redox active ligands into Ru(II) complexes often generates unique photochemical and electrochemical properties of the complexes.8a'16'17 As an extension of our work, we investigated the reaction of
the ligand TTF-terpy with Ru(II) precursors. In this paper, two novel ruthenium(II) complexes [Ru(TTF-terpy)(terpy)][PF6]2 (1) and [Ru(TTF-terpy)2][PF6]2 (2), were synthesized by coordination reactions of Ru(terpy) (dmso)2Cl2 or cis-Ru(dmso)4Cl2 with TTF-terpy, respectively (Scheme 1). Their spectroscopic and electrochemical properties were studied. The crystal structure of complex 1 is described.
2. Experimental
2. 1. Materials and Physical Measurements
Formyltetrathiafulvalene, Ru(dmso)4Cl2 and Ru-Cl2(terpy)dmso were synthesized according to the literature procedure.18 All solvents were purified by standard techniques prior to use. Moisture or air sensitive reactions were carried under a nitrogen atmosphere.
Elemental analyses for C, H and N were determined using a Perkin-Elmer 240C analyzer. Infrared spectra were recorded in the 400-4000 cm-1 region by Vector22 Bru-ker spectrophotometer with KBr pellets. Spectroelectroc-hemical measurements were performed in a thin-layer cell (optical length 0.2 cm) in which an ITO glass electrode was set in the indicated solvent containing the compound to be studied (the concentration is around 1 x 10-4 M) with 0.1 M Bu4NClO4as the supporting electrolyte. A platinum wire and Ag/AgCl in a saturated aqueous KCl solution were used as counter and reference electrodes, respectively. The cell was put into the spectrophotometer to monitor spectral changes during electrolysis. UV-VIS spectra were obtained on a UV-3100 spectrophotometer. Mass spectra were determined with an Autoflex II TM instru-
ment for ESI-MS. Cyclic voltammetry was performed on an Im6eX electrochemical analytical instrument, with a glassy carbon as the working electrode, platinum wire as the counter electrode, Ag/AgCl electrode containing sat. KCl served as the reference electrode, and 0.1 M n Bu4NClO4 as the supporting electrolyte.
2. 2. Preparation of [Ru(TTF-terpy)(terpy)]
[PF6]2 (1).
A mixture of RuCl2(terpy)dmso (48.5 mg, 0.1 mmol) and TTF-terpy (43.5 mg, 0.1 mmol) in 6 mL etha-nol was refluxed for 24 h. The solution was concentrated to about 2 mL, and then, KPF6 (92 mg, 0.5 mmol) in methanol (1 mL) was added. The solution was stirred for 30 min, and the solvent evaporated. The crude product was purified by column chromatography on silica gel (acetone: H2O: saturated aqueous KPF6 (v/v) 100 : 4 : 0.4). Complex 1 was isolated in 67% yield (71 mg) as a reddish-brown solid. IR (KBr, cm-1): 3061m, 2993w, 2909w, 1597m, 1583s, 1566s, 1535m, 1468m, 1449m, 1391s, 1083s, 1011m, 878m, 838s, 777s, 725m, 624m, 558s. ESI-MS, m/z: 385.3 [(M-2PF6)2+]/2. Anal. Calcd for C36H24F12N6P2RuS4: C, 40.79; H, 2.28; N, 7.93. Found: C, 40.89; H, 2.32; N, 7.86%.
2. 3. Preparation of [Ru(TTF-terpy)(terpy)]2 [PFJ2 (2).
A mixture of Ru(dmso)4Cl2 (48.4 mg, 0.1 mmol) and TTF-terpy (95.7 mg, 0.22 mmol) in 6 mL ethanol was ref-luxed for 24 h. The solution was concentrated to about 2 mL, and then KPF6 (92 mg, 0.5 mmol) in methanol (1 mL)
was added. The solution was stirred for 30 min, and the solvent evaporated. The crude product was purified by column chromatography on silica gel (acetone: H2O: saturated aqueous KPF6 (v/v) 100 : 4 : 0.4). Complex 2 was isolated in 58% yield (73 mg) as a brown solid. IR (KBr, cm1): 3058m, 3009w, 2920w, 2850w, 1598m, 1583s, 1566s, 1535s, 1467s, 1421m, 1394s, 1088m, 1013m, 877m, 842s, 787s, 726m, 658m, 633m, 558m. ESI-MS, m/z: 486.3 [(M-2PF6)2+]/2. Anal. Calcd for C42H26F12N6P2RuS8: C, 39.97; H, 2.08; N, 6.66. Found: C, 39.89; H, 2.14; N, 6.58%.
2. 4. X-ray Crystallography
The data were collected on a Bruker Smart Apex CCD diffractometer equipped with graphite-monochroma-ted Mo Ka (X = 0.71073 A) radiation using a w-2q scan
mode at 293 K. The collected data were reduced using the SAINT program,19 and multi-scan absorption corrections were performed using the SADABS program.20 The structures were solved by direct methods and refined against F2 by full-matrix least-squares methods using the SHELXTL.21 All non-hydrogen atoms were found in alternating difference Fourier syntheses and least-squares refinement cycles and, during the final cycles, refined aniso-tropically. All the hydrogen atoms were generated geometrically and refined isotropically using the riding model.
The solid structures of complex 1 were determined by single-crystal X-ray diffraction. The crystallographic and data collection parameters are given in Table 1; selected bond lengths and angles are listed in Table 2.
3. Results and Discussion
Table 1. Crystallographic data for 1.
1	
empirical formula	C38H27F!2N7P2RuS4
Mr	1100.92
Cryst system	monoclinic
Space group	P 21/c
a (Ä)	8.802(2)
b (Ä)	40.985(9)
c (Ä)	12.128(3)
a(°)	90.00
ß(°)	100.66(4)
r(°)	90.00
V (Ä3)	4299.7(17)
Z	4
Pc (gCm-3)	1.701
F(000)	2200
T / K	293(2)
^(Mo-KJ/ mm-1	0.725
Data / param. / restr.	8321 / 578 / 0
GOF	1.063
R1, wR2(I >2a(I))	0.0539 / 0.1326
R1, wR2 (all data)	0.0751 /0.1354
Large diff. peak / hole (e Ä-3)	0.447 / -0.386
3. 1. Synthesis and Characterization
The ligand TTF-terpy was prepared in one pot synthesis from formyltetrathiafulvalene, 2-acetylpyridine and ammonia in the presence of i-BuONa.11 Complexes 1 and 2 were obtained by reactions of TTF-terpy with Ru(terpy)(dmso)2Cl2 or Ru(dmso)4Cl2 in reflux ethanol solution, respectively. In the infrared spectra of 1 and 2, the sharp absorption bands of the counter anion (PF6") are located at 838 cm1 and 842 cm1, respectively. The positive ion electrospray mass spectra of these complexes are presented in Figures S1 and S2, they show full abundance of the parent peak which corresponds to {[(M-2PF6")]/2}+. Red crystals of complex 1 suitable for structure determination were obtained by diffusion of ether into an acetonitrile solution of 1.
3. 2. Crystal Structure Description of 1
Complex 1 crystallized in monoclinic system (space group P 21/c) and the asymmetric unit contains a complex cation, two PF6"anions and one CH3CN molecule. As shown in Figure 1, the Ru(II) adopts a distorted octahedral
Table 2. Selected Bond Distances (Â) and Angles (deg) for 1.
Ru(1)-N(1)	2.063(4)	Ru(1)-N(2)	1.956(4)
Ru(1)-N(3)	2.071(4)	Ru(1)-N(4)	2.045(4)
Ru(1)-N(5)	1.984(4)	Ru(1)-N(6)	2.069(4)
C(31)-C(32)	1.294(7)	C(33)-C(34)	1.292(7)
C(35)-C(36)	1.379(7)	C(33)-S(3)	1.775(5)
C(33)-S(4)	1.764(6)	C(34)-S(2)	1.757(6)
C(34)-S(1)	1.744(5)	N(1)-Ru(1)-N(3)	157.58(17)
N(2)-Ru(1)-N(4)	100.09(16)	N(2)-Ru(1)-N(6)	103.36(16)
N(4)-Ru(1)-N(5)	78.62(16)	N(5)-Ru(1)-N(6)	77.91(16)
N(1)-Ru(1)-N(2)	78.75(17)	N(1)-Ru(1)-N(4)	91.67(17)
N(1)-Ru(1)-N(5)	100.29(18)	N(1)-Ru(1)-N(6)	91.57(17)
N(3)-Ru(1)-N(2)	78.83(17)	N(3)-Ru(1)-N(4)	91.94(16)
N(3)-Ru(1)-N(5)	102.12(18)	N(3)-Ru(1)-N(6)	93.86(16)
Figure. 1. Thermal ellipsoid drawing with 50% probability of 1. Counter anions, H atoms and solvent are omitted for clarity.
geometry, with the equatorial plane defined by N1, N2, N3 and N5. The axial N6-Ru1-N4 angle of 156.51(17)° is significantly smaller than the ideal value of 180° caused by the shape of terpy units. While the sum of the equatorial angles N5-Ru1-N3, N3-Ru1-N2, N2-Ru1-N1, and N1-Ru1-N5 for complex 1 (« 354.99°) is very close to the ideal value (360.00°), which ensures the planarity of equatorial plane. Among the Ru-N bond lengths, the bond distance of Ru(II) to the central terpy nitrogen (Ru1-N2, being 1.956(4) À, and Ru1-N5, being 1.984(4) À] is ca. 0.1 À shorter than the other Ru-N distances (2.045(4)-2.071(4) À), which is typical feature in the structure of other terpy-Ru(II) complexes.17a The corresponding Ru-N bond lengths and angles in complex 1 are comparable to those found in similar Ru(terpy)22+ complexes, such as [Ru(terpy)(bpy')Cl]PF6 (bpy' = 4-carboxy-4'-methyl-2,2'-bipyridine derivatives) 22a, [Ru(terpy) (PDA-N,N')-(OH2)](ClO4)2 (PDA = 6-acetonyl-6-hy-droxy-1,10-phenanthroline-5-one).22b
Complex 1 contains mutually orthogonal ligands, the TTF-terpy coordination plane (N4, N5, N6 and Ru1) forms a dihedral angle of 89.34(1)° with the terpy coordination plane (N1, N2, N3 and Ru1). The five-membered ring (C31, S4, C33, S3, C32) is twisted out of the TTF-terpy coordination plane by 15.59(6)°. The TTF skeleton itself is almost planar, and the average deviation from a least-squares plane is 0.0300 À. In addition, the dihedral angle between the two five-membered rings is only
2.84(1)°. The central C=C bond length of the TTF core is 1.292(7) A, which is within the normal range for a neutral molecule.23'24
In the solid state, the molecules of 1 are stacked in a head-tail fashion. The adjacent five-membered ring (containing S4, S3) and pyridine ring (containing N4) are approximately parallel to each other (the dihedral angle is 1.21(5)°), with a center-center distance of 3.720(6) A, indicating the presence of face-to-face n - n stacking interactions, which further connect the molecules into one-dimensional chainlike structure along the c axis (Figure 2).
Figure. 2. rc-rc stacking interactions found in 1 (H atoms are omitted for clarity).
Figure. 3. Cyclic voltammograms for TTF-terpy, complexes 1 and 2.
3. 3. Electrochemical Properties
The redox properties of 1 and 2 were investigated using cyclic voltammetry in CH2Cl2/CH3CN (1:1 ratio, 0.1 mol ■ L-1 n-Bu4NClO4). As shown in Figure 3, three one-electron oxidation waves were observed in the potential region 0.0 to + 1.8 V (vs Ag/AgCl). A comparison of their redox behaviors to that of TTF-terpy indicates that the first two oxidations around 0.48 V (£1/21) and 0.83 V (E1/22) are TTF based, which are derived from the successive oxidation of neutral TTF (TTF0) to the radical cation (TTF+) and then to the dication (TTF2+). Compared with the ligand TTF-terpy, upon complexation, the first oxidation potential is shifted to slightly more positive potential, which is the same as {TTF-Re(I)},4b, 4c (TTF-[Ru3(^3-O)]} complexes,25 caused by the electron-withdrawing inductive effect of the metal core. However, the second oxidation potential is negatively shifted by 20 mV. This shift can be explained by the electronic interactions between the TTF unit and the Ru(terpy) unit caused by the shorter distance between them.11 The third redox process at about E1/23 = 1.37 V can be assigned to the Ru(II)-centered one-electron oxidation process.16a
3. 4. Spectroscopic Properties
6
0 -1-i-1-i-1-■-1-- — . —
300	400	500	600	700
Wavelength (nm)
Figure. 4. Absorption spectra of 1 and 2 (1 X 10-5 M) in CHjCjj/CHjCN (1:1 ratio).
The absorption spectra of complexes 1 and 2 in CH2Cl2/CH3CN (1:1 ratio) at room temperature were measured. As depicted in Figure 4, intense absorptions relating to the admixture of intraligand (tc^tc*) transitions of the TTF moiety and the terpy moiety are observed in the range of 255-350 nm, which are red-shifted (about 35-41 nm) and more intense compared with the free li-gand TTF-terpy. The red shift is reasonable since the energy of the LUMO localized on the terpy unit is lowered upon coordination to Ru(II).4c In addition, complexes 1 and 2 also display broad bands at lower energy (350-650 nm), which could be assigned to the admixture of metal-to-ligand charge-transfer (MLCT, dn(Ru)^n*(TTF-ter-py)) and ligand-to-ligand charge-transfer (LLCT) transitions.11,26
Spectroelectrochemical measurements were also carried out during the electrolysis of the solution of complexes 1 and 2 in CH2Cl2/CH3CN (1:1 ratio) at suitable
300 400	500	GOO	700
Wavelength (nm)
Figure. 5. Spectroelectrochemistry of 1 in CH2Cl2/CH3CN (1:1) (0.1M Bu4NClO4).
constant potentials corresponding to its redox processes (Figures 5 and S3). The first stage of the electrochemical oxidation leads to the appearance of TTF radical cation bands around 448 nm. Upon the application the potential of 1.3 V, the electronic spectra show a decrease in the characteristic absorption of the radical cation bands (TTF+-terpy) and the appearance of dication bands (TTF2+-terpy) around 330-410 nm.
4. Conclusion
In summary, with the versatile ligand TTF-terpy, two novel ruthenium(II) complexes 1 and 2 were synthesized. The electrochemistry measurements suggested that these compounds display rich redox processes. On comple-xation, the two oxidation peaks of TTF backbone in 1 and 2 exhibit different shifts caused by electronic interactions between the TTF unit and the Ru(II) core. The electronic properties in the neutral TTF-terpy based compounds as well as in the radical cation TTF+-terpy and dication species TTF2+-terpy based compounds have been studied by spec-troelectrochemical and absorption spectra. The results show that the versatile n-conjugated terpyridine ligand is useful for the preparation of multifunctional materials, and further work for exploring interesting conducting and magnetic materials is going on in our laboratory.
5. Supplementary Information
Crystallographic data (excluding structure factors) for the structural analysis have been deposited with the Cambridge Crystallographic Data Center as supplementary publication Nos. CCDC 977059 (1). Copies of the data can be obtained free of charge via www.ccdc.ac.uk/con-ts/retrieving.html (or from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, Fax: +44-1223-336033. E-mail: deposit@ccdc.cam.ac.uk.).
6. Acknowledgments
This work was supported by the Major State Basic Research Development Program (2011CB808704 and 2013CB922101), and the National Natural Science Foundation of China (21021062 and 21301108).
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Povzetek
Dva nova rutenijeva(II) kompleksa [Ru(TTF-terpy)(terpy)][PF6]2 (terpy = 2,2 :6 ,2 -terpyridine) (1) in [Ru(TTF-ter-py)2][PF6]2 (2) sta bila sintetizirana z reakcijo Ru(terpy)(dmso)2Cl2 oziroma c/i-Ru(dmso)4Cl2 s 4-tetratiafulvalen-2,2 :6 ,2 -terpiridinom (TTF-terpy). S pomočjo rentgenske difrakcije je bila določena kristalna struktura 1. V kristalu spojine 1 so molekule povezane v 1D verigo preko %■■■% interakcij. Elektrokemijske in spektroskopske lastnosti spojin so bile proučene. Rezultati kažejo postopen redoks proces Ru(II) kompleksov v raztopini in so obetavni gradniki večfunkcionalnih materialov.
Syntheses, Characterization, and Properties of Ru(II) Complexes Based on n-conjugated Terpyridine Ligand with Tetrathiafulvalene Moiety
Jie Qin,12 * Liang Hu,2 Na Lei,1 Yan-Fei Liu,1 Ke-Ke Zhang1
and Jing-Lin Zuo2
1 School of Life Sciences, Shandong University of Technology, Zibo, China
2 State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering,
Nanjing University, Nanjing, China
* Corresponding author: E-mail: qinjietutu@ 163.com
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486.17
4 -."A I	I T
450	500	550
617.17
450 mfc
t -fr T 'r*VV r*f*
600	650
363.33 713.08 771.00
799.00
-1" r-i'T"*T-fVTTf"i"f''|
700	750	800
Fig. SI. ESI-MS of complex 1.
Fig. S2. ESI-MS of complex 2.
Fig. S3. Spectroelectrochemistry of 2 in CH2Cl2/CH3CN (1:1) (0.1M Bu4NClO4).