CRYSTAL GROWTH & DESIGN
Tetrathiafulvalene-Diamide Salts with S‚‚‚S and C‚‚‚C Stacked Radical Couples Lu,†
Wen Qin-Yu De-Qing Zhang‡
Zhu,†
Jie
Dai,*,†
Yong
Zhang,†
Guo-Qing
Bian,†
Yu
Liu,†
2007 VOL. 7, NO. 4 652-657
and
Department of Chemistry & Key Laboratory of Organic Synthesis of Jiangsu ProVince, Suzhou UniVersity, Suzhou 215123, P. R. China and Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China ReceiVed July 25, 2006; ReVised Manuscript ReceiVed NoVember 22, 2006
ABSTRACT: Three new radical salts, [DMT-TTF-(CONHMe)2]2CuBr4 (2), DMT-TTF-(CONHMe)2‚ClO4 (3), and DMT-TTF(CONHMe)2‚Br (4), have been obtained by reacting DMT-TTF-(CONHMe)2 (1) with CuBr2 and Cu(ClO4)2 (DMT-TTF ) dimethylthio-tetrathiafulvalene). The [DMT-TTF-(CONHMe)2]•+ cations of the three compounds are self-assembled to cation couples with short S‚‚‚S and C‚‚‚C stackings. Radical coupling was found within these TTF dimers, the intensity of which is related to the stacking distance between the coupled TTF molecules. When the S‚‚‚S stacking is of a comparative intensity, the C‚‚‚C stacking distance will play an important role in the antiferromagnetical coupling of the radicals. The intensity of the radical signals in electron spin resonance (ESR) was found to be in the order 2 < 3 < 4, which is related to the π‚‚‚π stacking distance of the central CdC bonds of the TTF moieties. The stronger the C‚‚‚C interactions are, the weaker the radical signal becomes in the ESR spectra. Introduction Recently, due to the capacity of amides to produce a regular arrangement of molecules through self-complementary association, researchers have showed interest in the preparation of tetrathiafulvalenes (TTFs) functionalized with amide substituents. Some monocomponent molecular solids and radical salts based on these TTF derivatives have been synthesized and characterized.1,2 TTF derivatives with a mono-amide group have been first reported by Bryce et al.,1 and some radical cation salts, such as [EDT-TTF-CONH2]2ReO4 and [EDT-TTFCONH2]6AsF6,2b have been reported by Batail et al. in 1998 (EDT-TTF ) ethylenedithio-tetrathiafulvalene). Lately, a series of diamide-TTF derivatives, EDT-TTF-(CONHR)2 (R ) H, Me, Et, Pr, Py, bipy, etc), were synthesized, and their radical salts have also been studied.2c-2e The incorporation of hydrogen bonds and S‚‚‚S intermolecular interactions in these compounds is one of the important factors for directing the solid-state chemistry and modifying the collective electronic properties of the molecular solids.2c,2f,2g The S‚‚‚S interaction exists widely in radical salts or charge-transfer compounds of TTFs, and, up to now, numerous studies have been reported on the crystal engineering of TTF materials.3 The TTF units are assembled into columns or dimers in these crystals with two types of S‚ ‚‚S interactions. One is S‚‚S stacking, in which the TTF units interact in a face-to-face arrangement, and the other is S‚‚‚S contact, in which the TTF units interact in a side-by-side arrangement. Short S‚‚‚S stacking within the TTF dimers is related to both magnetic properties and electric conductivity, which has been long-established by experimental and theoretical chemists.3a-c,4 Nevertheless, in contrast to the importance of S‚‚‚S stacking, π‚‚‚π stacking of carbon atoms between the central CdC bonds of TTF molecules has rarely been discussed, because in TTF salts or compounds the C‚‚‚C distance is usually * To whom correspondence should be addressed. Department of Chemistry, Suzhou University, Suzhou 215123, P. R. China. Fax: +86 (0)512 65880089. E-mail:
[email protected]. † Department of Chemistry & Key Laboratory of Organic Synthesis of Jiangsu Province, Suzhou University. ‡ Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences.
longer than the recognized sum of the van der Waals radii of two carbon atoms (about 3.40 Å), and thus the orbital interactions within TTF molecules are mainly located on the sulfur atoms. Herein, we present the synthesis and crystal structures of three new radical cation salts of o-bis(methylamide)-appended dimethylthio-TTF, DMT-TTF-(CONHMe)2 (1) (DMT-TTF ) dimethylthio-tetrathiafulvalene). The inter-radical coupling in TTF dimers is found to be related not only to the S‚‚‚S stacking but also to the C‚‚‚C stacking between the central CdC bonds of TTF molecules.
Experimental Section General Remarks. The raw material, 1,2-bis(methyl-carboxylate)3,4-bis(methylthio)-tetrathiafulvalene, C12H12O4S6, was synthesized by a coupling method as reported.5 The precursor, 1,2-bis(methylamide)3,4-bis(methylthio)-tetrathiafulvalene, DMT-TTF-(CONHMe)2 (1), was synthesized using a method reported previously.2c Elemental analyses of C, H, and N were performed using an EA 1110 elemental analyzer. The IR spectra were recorded as KBr discs on a Nicolet Magna 550 FT-IR spectrometer. ESR spectra were recorded on an EMX-10/12 spectrometer at 110 K. Cyclic voltammetry (CV) was performed on a model CHI600 electrochemistry workstation, with a cell containing a Pt plate as the working electrode, a Pt wire as the counter electrode, and a saturated calomel electrode (SCE) as the reference electrode. Tetrabutyl-ammonium perchlorate was used as electrolyte, and HPLCgrade solvents were used for electrochemical measurements. Synthesis of Compounds. [C12H14O2N2S6]2CuBr4 (2). An acetonitrile solution (6 mL) of CuBr2 (44.6 mg, 0.2 mmol) was slowly dropped to a THF solution (2 mL) of precursor 1 (8.3 mg, 0.02 mmol), and then the mixed solution was kept at room temperature for several hours. Black crystals suitable for X-ray crystal determination were obtained, washed with acetonitrile, and finally dried in vacuo (yield: 10.23 mg, 48%). IR (cm-1), 3425 (NH), 3245 (NH), 1661 (CdO), 1644 (CdO),1345 (CdC). C24H28N4O4S12CuBr4 (1204.40): calcd C 24.03, H 2.35, N, 4.67%; found: C 23.39, H 2.34, N 4.65%. [C12H14O2N2S6]ClO4 (3). To a methanol solution (2.0 mL) of Cu(ClO4)2 (37.1 mg, 0.1 mmol) was added precursor 1 (8.3 mg, 0.02
10.1021/cg060490s CCC: $37.00 © 2007 American Chemical Society Published on Web 02/22/2007
Tetrathiafulvalene-Diamide Salts
Crystal Growth & Design, Vol. 7, No. 4, 2007 653 and finally dried in vacuo (yield: 8.14 mg, 38%). IR (cm-1), 3434 (NH), 3218 (NH), 1651 (CdO), 1328(CdC). [C12H14O2N2S6]Br (490.52): calcd. C 29.50, H 2.48, N 5.73%; found C 28.97, H 2.78, N 5.50%. X-ray Crystallographic Study. All measurements were carried out on a Rigaku Mercury CCD diffractometer at 193 or 173 K with graphite monochromated Mo-KR (λ ) 0.71073 Å) radiation. X-ray crystallographic data for compounds 2-4 were collected and processed using CrystalClear (Rigaku).6 The structures were solved by direct methods using SHELXS-97,7 and the refinements against all reflections of the compounds were performed using SHELXL-97.8 All the non-hydrogen atoms were refined anisotropically. The hydrogen atoms were positioned with idealized geometry and refined with fixed isotropic displacement parameters, while the H(1) and H(2) atoms of the 2 were located from the map.
Scheme 1
mmol) in dichloromethane (1.0 mL). After the solution was stirred for 2 h at room temperature, the mixture was diffused with diethylether in a straight tube. Black crystals suitable for X-ray crystal determination were obtained on the tube wall after 1 day, washed with acetonitrile, and finally dried in vacuo (yield: 10.18 mg, 45%). IR (cm-1), 3434 (NH), 3218 (NH), 1651 (CdO), 1328 (CdC). [C12H14O2N2S6]ClO4 (510.06): calcd. C 28.26, H 2.74, N 5.49%; found C 28.56, H 2.86, N 5.06%. [C12H14O2N2S6]Br (4). To an acetonitrile solution (1.0 mL) of CuBr2 (2.3 mg, 0.01 mmol) was added a solution of the precursor 1 (12.6 mg, 0.03 mmol) in THF (2.0 mL), and then the mixed solution was kept at room temperature for several hours. Black crystals suitable for X-ray crystal determination were obtained, washed with acetonitrile,
Results and Discussion Synthesis and Characterization. Most crystals of radical salts of TTF-diamide systems are prepared by means of electrocrystallization, and a majority of them are partly oxidized. Scheme 1 shows the synthetic routes for compounds 2-4, which are prepared by direct chemical oxidization. The TTF precursor 1 is one-electron oxidized to 1•+ by Cu(II) ions for all these
Table 1. Crystallographic Data for Compounds 2-4
a
compound
2
3
4
empirical formula formula mass color, habit crystal system crystal size [mm] space group a [Å] b [Å] c [Å] R [˚] β [˚] γ [˚] Z T [K] V [Å3] Dcalc [mg m-3] F (000) reflections collected unique reflections R1 [I > 2(I)]a wR2a goodness of fit
[C12H14O2N2S6]2CuBr4 1204.40 black, strip monoclinic 0.50 × 0.19 × 0.15 C2/c 24.140(3) 11.7092(12) 14.2102(17) 90 98.537(3) 90 4 193(2) 3972.2(8) 2.014 2372 21856 4552 0.0406 0.0924 1.094
[C12H14O2N2S6]ClO4 510.06 black, strip triclinic 0.60 × 0.25 × 0.15 P1h 7.4716(11) 10.4775(16) 13.571(2) 112.049(3) 91.326(2) 99.671(3) 2 173(2) 966.4(3) 1.753 522 8950 3488 0.0325 0.0807 1.016
[C12H14O2N2S6]Br 490.52 black, strip monoclinic 0.30 × 0.11 × 0.06 P21/n 7.1863(9) 25.310(3) 10.2043(12) 90 107.645(3) 90 4 173(2) 1768.7(4) 1.842 988 17232 3237 0.0319 0.0633 1.154
R1 ) ∑ |Fo| - |Fc|/∑ |Fo and wR2 ) [∑(w(Fo2 - Fc2)2)/∑w(Fo2)2]1/2. Table 2. Selected Bond Lengths (Å) and Angles (deg) and the Important Interaction Distances for 2-4a 2
C(3)-S(2) C(3)-S(1) C(4)-S(3) C(4)-S(4) C(3)-C(4) C(1)-C(2) C(5)-C(6) O(1)-C(9) O(2)-C(11) O(1)-C(9)-N(1) O(2)-C(11)-N(2) Br(2)-Cu(1)-Br(2ii) Br(2)-Cu(1)-Br(1ii) C(2)-C(1)-C(9)-N(1) C(1)-C(2)-C(11)-N(2) O(2)‚‚‚S(6i) S(2)‚‚‚S(4ii) S(1)‚‚‚S(1ii) C(3)‚‚‚C(4ii) a
3 1.744(3) 1.739(3) 1.733(3) 1.726(3) 1.389(4) 1.352(5) 1.366(5) 1.239(4) 1.234(4) 124.7(3) 124.3(3) 122.03(4) 107.90(2) 12.8(5) 133.8(4) 3.2886(26) 3.3754(12) 3.5720(13) 3.3572(13)
4
C(3)-S(1) C(3)-S(2) C(4)-S(3) C(4)-S(4) C(3)-C(4) C(1)-C(2) C(5)-C(6) O(1)-C(7) O(2)-C(9) O(1)-C(7)-N(1) O(2)-C(9)-N(2)
1.750(2) 1.746(2) 1.730(2) 1.727(2) 1.393(3) 1.355(3) 1.373(3) 1.228(3) 1.237(3) 122.5(2) 125.8(2)
C(3)-S(1) C(3)-S(2) C(4)-S(3) C(4)-S(4) C(3)-C(4) C(1)-C(2) C(5)-C(6) O(1)-C(7) O(2)-C(9) O(1)-C(7)-N(1) O(2)-C(9)-N(2)
1.757(3) 1.748(3) 1.729(3) 1.728(3) 1.389(4) 1.359(4) 1.386(4) 1.229(3) 1.235(3) 122.6(3) 125.3(3)
C(1)-C(2)-C(9)--N(2) C(2)-(1)-C(7)-N(1) O(1)‚‚‚S(6iii) S(2)‚‚‚S(3iv) S(1)‚‚‚S(4iv) C(3)‚‚‚C(4iv)
17.2(4) 161.7(2) 3.1267(21) 3.2814(10) 3.4675(10) 3.3975(33)
C(1)-C(2)-C(9)-N(2) C(2)-(1)-C(7)-N(1) S(2)‚‚‚(3v) S(1)‚‚‚S(4v) C(3)‚‚‚C(4v) C(3)‚‚‚C(3v)
18.3(5) 164.4(3) 3.3958(12) 3.4806(12) 3.4775(44) 3.413(4)
i: x - 1/2, y + 1/2, z; ii: -x + 1, y, -z + 1/2; iii: x, y, z - 1; iv: -x + 1, -y + 1, -z + 1; v: -x + 1, -y + 1, -z + 1.
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three compounds in the synthetic reactions. It is well-known that copper(II) ions can oxidize the TTF derivatives readily, providing a variety of charge-transfer (CT) salts.4,9 The Cu(II) ion is reduced to Cu(I), while the Cu(I) ion tends to be reoxidized to Cu(II) under ambient conditions. Crystals of compounds 2 and 4 were obtained by a slow evaporating method using the same reactants and solvents (THF/CH3CN) at room temperature, but the ratio of the reactants (1/CuBr2) was changed. Differing from 2 and 4, crystals of compound 3 were obtained in a mixed solvent, CH3OH/CH2Cl2, using diethylether as the diffusion solvent. The one-electron oxidization of 1 can be confirmed by the IR stretching band of the central CdC bond of the TTF unit, which are observed at 1345, 1328, and 1328 cm-1 for compounds 2-4, respectively, showing a red shift contrasted to 1403 cm-1 for the neutral 1. It is known that the central CdC bond stretching of TTF undergoes a large frequency shift on oxidation (about 50-100 cm-1).10 Considering the results of elemental analyses, spectrometry and the stoichiometry, the charge distribution might be deduced as [(TTF•+(CONHCH3)2)2(CuBr42-)], [(TTF•+(CONHCH3)2) (ClO4-)], and [(TTF•+(CONHCH3)2)Br-], which have been confirmed by X-ray crystal characterization. Description of the Structures. Compounds 2-4 are chargetransfer salts formed with 1•+ cation and CuBr42-, ClO4-, Branions, respectively. The compounds crystallized in the monoclinic (2, 4) and triclinic (3) systems with space group C2/c, P1h, and P21/n, respectively. A summary of the experimental details and selected results for compounds 2-4 are given in Table 1. The selected bond distances and angles are listed in Table 2. ORTEP diagrams of these TTF derivatives are shown in Figure 1. There is intramolecular hydrogen bond (N-H‚‚‚ O) between the two ortho amide groups in all these compounds. The TTF moieties in the salts are nearly planar, which is different from the boat-shaped structure usually found in neutral derivatives of TTF. The central CdC distances of the TTF units, C(3)-C(4), are 1.389, 1.393, and 1.388 Å, respectively, and the average S-CCdC distance of the heterocycles is about 1.738 Å, which confirms the oxidized character of the TTF donor core compared with those distances found in the neutral TTF compounds and the TTF•+ radicals.2i,2c,4b, 11 The TTF cations in the three compounds are self-assembled into molecular couples with short S‚‚‚S stacking, which is usually found in radical compounds of TTFs.3 Figure 2 illustrates the TTF dimers in these compounds. Besides the S‚‚‚S stacking, carbon-carbon π stacking of the central CdC bond was also found within these dimers for compound 2 and 3 with distance 3.357 and 3.397 Å, respectively, while the corresponding distance of 4 is 3.478(4) Å, which is weaker than the former. Between the couples, there are short S(methylthio)‚‚O(amide) contacts (3.289 Å) in compound 2. Every couple connects with four neighboring couples by these S‚‚‚O interactions, forming a bilayered two-dimensional network (Figure 3). The compound 3 self-assembled to a one-dimensional chain structure with such a S‚‚‚O short contact (3.127 Å). These important distances of the weak interactions in 2-4 are listed in Table 2. Other weak hydrogen bonds and cation-anion interactions are also important factors in governing the solid-state arrangement in complementing S‚‚‚S and π‚‚‚π interactions (Supporting Information Figures SI-1 and SI-2). π‚‚‚π Stacking of the Central CdC Bonds. It has been mentioned that there are C‚‚‚C short stackings between the central CdC bonds of the TTF units in molecular couples of 2 and 3 (3.357 and 3.397 Å, respectively, Figure 2 and Table 2), while the corresponding distance of 4 is 3.478(4) Å. Considering
Lu et al.
Figure 1. ORTEP digrams of the TTF salts 2-4 with the labeling scheme. Displacement ellipsoids are drawn at the 40% level, and hydrogen atoms are omitted for clarity.
that the commonly recognized distance of C‚‚‚C interactions is about 3.40 Å (the sum of the van der Waals radii of the corresponding two carbon atoms), the interaction of central Cd C bonds in 4 is weaker than those in 2 and 3. Although the shortest C‚‚‚C distance in 4 is 3.413(4) Å, C(3)‚‚‚C(3v), only slightly longer than 3.397(3) Å in 3, C(3)‚‚‚C(4iii), the interaction mode in 4 is different from those in 2 and 3 (Figure 4). The interactions of CdC π-bonds in 2 and 3 are completely overlapped, while it is not for compound 4, which reduces the efficiency of the C‚‚‚C interaction. Solid-state ESR spectra (polycrystalline sample) were measured at 110 K, and the results are revealed in Figure 5. The radicals in the dimer of 2 are strongly antiferromagnetically coupled, and therefore no sharp radical signal is observed from the ESR spectrum, which only shows a parallel and perpendicular split of Cu(II) character, CuBr42- anion, with g values
Tetrathiafulvalene-Diamide Salts
Crystal Growth & Design, Vol. 7, No. 4, 2007 655
Figure 4. The modes of C‚‚‚C stackings in TTF salts 2-4.
Figure 2. The cation couples in TTF salts 2-4, showing the S‚‚‚S and C‚‚‚C stackings.
Figure 5. Solid-state ESR spectra measured at 110 K: (a) compound 2; (b) compound 3 (red line) and compound 4 (black line).
Figure 3. The double-layered two-dimensional network assembled by cation couples of 2.
of 2.246 and 2.048 for g| and g⊥ values, respectively (Figure 5a). The ESR spectra of compound 3 and 4 show a radical signal of high intensity at 2.012 for the g value (Figure 5b), in which the strongest one belongs to compound 4. We observed that the intensity of the radical signals, in the order 2 < 3 < 4, is related to the CdC stacking distance. The strongest signal of
compound 4 is attributed to its very weak C‚‚‚C stacking (3.478 Å) between the CdC bonds. In contrast, compound 2 shows the shortest π‚‚‚π stacking (3.357 Å), which complements the S‚‚‚S stacking resulting in strong coupling of the radicals (no radical signal). There is also C‚‚‚C stacking in compound 3, but its distance of 3.397 Å is longer than that of 2. Therefore, it shows radical signal, but it is not so strong as that of 4. To ensure the rationality of the discussion above, the HOMO orbit of 1 and the spin density in SOMO of 1•+ have been calculated and depicted in Figure 6. The results are in accordance with those reported.4a,12 The orbit density or spin density on CdC bond are comparable to those on sulfur atoms, and therefore when the S‚‚‚S stacking of the compounds is of comparative intensity, the C‚‚‚C stacking distances will be important data for the antiferromagnetical coupling of the radicals. Redox Chemistry of the TTF Derivatives. The cyclic voltammetry of 1 was studied in acetonitrile containing 0.1
656 Crystal Growth & Design, Vol. 7, No. 4, 2007
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Figure 8. UV-vis-NIR spectra in CH3CN, (a) black line, compound 1 (5.0 × 10-5 M); (b) green line, CuBr2 (5.0 × 10-4 M); (c) red line, 1.0 × 10-3 M CuBr2 was added to 1 (5.0 × 10-5 M).
Figure 6. The HOMO orbit of 1 (a) and the spin density of 1•+ (b).
Br (4), were obtained by reacting DMT-TTF-(CONHMe)2 (1) with CuBr2 and Cu(ClO4)2. Their crystal structures have been characterized with respect to the van der Waals interactons. The TTF cations in these three compounds are self-assembled to molecular couples with short S‚‚‚S and C‚‚‚C stacking. The intensity of the radical signals in ESR was found in the order 2 < 3 < 4, which is related to the π‚‚‚π stacking distance of the CdC bonds in the TTF dimer. When the S‚‚‚S stacking is of comparative intensity, the stronger the C‚‚‚C interaction is, the weaker the radical signal becomes, in the ESR spectra. Primary theoretical calculations also support the possibility of the results. However, substantive information both from experimental and theoretical studies is needed to provide a detailed knowledge of C‚‚‚C interaction in these TTF salts. Acknowledgment. This work was supported by the National Natural Science Foundation (20371033) P. R. China. The authors are also grateful to the State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, P. R. China, for technical support.
Figure 7. Cyclic voltammograms of compound 1 (1.0 × 10-3 M) in CH3CN, black line (a); 1.0 × 10-3 M CuBr2 was added to 1, red line (b).
mol‚dm-3 Bu4NClO4. Two couples of reversible redox peaks were detected (Figure 7, black line). The E1/2(1) and E1/2(2) of 1 are 0.517 and 0.803 V vs SCE. When CuBr2 is added into the above solution, the redox peaks (red line) shift by 44 mV (∆E1/2(1)) and 20 mV (∆E1/2(2)) respectively toward more positive potentials. According to the shifts, it is obvious that there are strong interactions between the TTF derivative and copper(II) bromide even in the solution. A pair of weak redox peaks at about 1.0 V should be the redox of the bromide ion. The corresponding results of the electronic absorption spectra are given in Figure 8. The red line is the spectrum recorded when CuBr2 is add into the acetonitrile solution of 1. Compared to the absorption of 1 and CuBr2, the new broad charge-transfer peak at around 800 nm should be assigned to the TTF•+ radical.13 Conclusion Three new radical salts, [DMT-TTF-(CONHMe)2]2CuBr4 (2), DMT-TTF-(CONHMe)2‚ClO4 (3), and DMT-TTF-(CONHMe)2‚
Supporting Information Available: Crystallographic data of 2-4 in CIF format; molecular packing structures of compounds 3 and 4. This information is available free of charge via the Internet at http:// pubs.acs.org.
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