Sulfur-containing mixed-donor tribenzo-macrocycles and their endo-and exocyclic supramolecular silver(I) and copper(I) complexes

Article abstract of DOI:10.1021/ic1007473

New sulfur-containing mixed-donor macrocycles L¹-L⁴ with different donor sets and/or ring sizes (L¹, 20-membered O ₃S₂; L², 20-membered NO₂S ₂; L³, 20-membe

Full text of DOI:10.1021/ic1007473

7510 Inorg. Chem. 2010, 49, 7510–7520
DOI: 10.1021/ic1007473
Sulfur-Containing Mixed-Donor Tribenzo-Macrocycles and Their Endo- and
Exocyclic Supramolecular Silver(I) and Copper(I) Complexes
Eun-Ju Kang, So Young Lee, Hayan Lee, and Shim Sung Lee*
Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University,
Jinju 660-701, South Korea
Received April 19, 2010
New sulfur-containing mixed-donor macrocycles L1-L4 with different donor sets and/or ring sizes (L1, 20-membered
O3S2; L2, 20-membered NO2S2; L3, 20-membered O2S3; and L4, 23-membered O4S2) were synthesized and
structurally characterized by X-ray analysis. A comparative investigation of the coordination behavior of these
macrocyclic ligands with silver(I) salts and copper(I) iodide is reported. The X-ray structures of seven complexes
(1-7) have been determined, and a range of structural types and coordination modes, including mono- to multinuclear
and endo- to exocyclic ones via M-S bonds, is shown to occur. In all seven complexes, the ether oxygens of each ring
are unbound. Reactions of L1-L4 with the silver(I) salts (ClO4-, BF4-, and NO3-) afforded four complexes with
different topologies: the exocyclic 1-D coordination polymer [Ag(L1)(ClO4)]n (1), the endocyclic 1:1 monomer complex
[Ag(L2)]ClO4 CH3OH (2), the endo-/exocyclic 1-D coordination polymer {[Ag2(L2)(CH3OH)](BF4)2}n (3), and the
3
cyclic dimer complex [Ag2(L3)2(NO3)2] 2CH3CN (4). NMR titrations of L1 and L2 with silver(I) perchlorate were
carried out to explore their complexation behavior in solution and also for comparison with the solid state structures. As
3
well, reaction of the above ligands with copper(I) iodide afforded the exocyclic dimer, [Cu2I2(L1)2] CH2Cl2 (5), linked
3
with diamond-type Cu-I2-Cu unit, the exocyclic monomer complex [CuI(L3)] CH2Cl2 (6), and the emissive 1-D
3
poly(cyclic dimer) complex {[Cu4I4(L4)2] CH2Cl2}n (7) linked by a cubane-type Cu4I4 unit. The formation of both the
discrete and continuous supramolecular complexes with copper(I) iodide is discussed in terms of a ligand-directed
“sulfur-to-sulfur” distance effect.
3
Introduction
changes in the coordination geometries of the corresponding
Ag(I) complexes.3 Clearly, such behavior reflects the differ-
ence in hardness, polarizability, and affinity toward Ag(I) of
the different X donors. In view of this, it was of interest to
explore the possible related behavior of these ligands toward
copper, which in its þ1 state also has a d10 electronic con-
figuration.3a We also proposed that tuning of the sulfur-to-
sulfur distance in dithiamacrocycles is effective for discrimi-
nating the product because of the different exocoordination
modes for silver(I) and mercury(II) ions.4 The coordination
of copper(I) halide with such ligand systems is also of parti-
cular interest given the previously documented diverse bind-
ing modes displayed by this ion toward dithiamacrocycles
and the unique photophysical properties often exhibited by
the metal complexes so generated.5
Sulfur-donor macrocycles (or thiamacrocycles) often show
unusual coordinating behavior toward soft d-block metal
ions, giving rise to supramolecular complexes with diverse
topologies. Frequently in these, the metal ion is forced to
adopt an unusual environment due to exocyclic coordi-
nation.1 For example, such exodentate coordination tends
to lead to the formation of coordination polymers with un-
usual structures, as well as to discrete metallo suprastructures
bearing less-common stoichiometries.2
We have recently reported that variation of the X donor in
O2S2X macrocycles (X = S, NH, or O) triggers marked
*To whom correspondence should be addressed. E-mail: sslee@gnu.ac.kr.
(1) (a) Wolf, R. E., Jr; Hartman, J. R.; Storey, J. M. E.; Foxman, B. M.;
Cooper, S. R. J. Am. Chem. Soc. 1987, 109, 4328. (b) Hill, S. E.; Feller, D.
J. Phys. Chem. A 2000, 104, 652.
ꢀ
(2) (a) Valencia, L.; Perez-Lourido, P.; Bastida, R.; Macıas, A. Cryst.
(4) (a) Lee, S. Y.; Park, S.; Kim, H. J.; Jung, J. H.; Lee, S. S. Inorg. Chem.
2008, 47, 1913. (b) Lee, S. Y.; Seo, J.; Yoon, I.; Kim, C.-S.; Choi, K. S.; Kim, J. S.;
Lee, S. S. Eur. J. Inorg. Chem. 2006, 3525. (c) Park, S.; Lee, S. Y.; Jo, M.; Lee,
J. Y.; Lee, S. S. CrystEngComm. 2009, 11, 43.
(5) (a) Lee, J. Y.; Lee, S. Y.; Sim, W.; Park, K.-M.; Kim, J.; Lee, S. S.
Inorg. Chem. 2008, 130, 6902. (b) Graham, P. M.; Pike, R. D. Inorg. Chem. 2000,
39, 5121. (c) Babich, O. A.; Kokozay, V. N. Polyhedron 1997, 16, 1487.
(d) Vitale, M.; Palke, W. E.; Ford, P. C. J. Phys. Chem. 1992, 96, 8329.
(e) Churchill, M. R.; Rotella, F. J. Inorg. Chem. 1977, 16, 3267.
Growth Des. 2008, 8, 2080. (b) Tiekink, E. R. T.; Vittal, J. J. Frontiers in Crystal
Engineering; Wiley: Chichester, 2006. (c) Oh, M.; Carpenter, G. B.; Sweigart,
D. A. Acc. Chem. Res. 2004, 37, 1. (d) Lee, S. Y.; Park, S.; Lee, S. S. Inorg.
Chem. 2009, 48, 11335.
(3) (a) Jo, M.; Seo, J.; Seo, M. L.; Choi, K. S.; Cha, S. K.; Lindoy, L. F.;
Lee, S. S. Inorg. Chem. 2009, 48, 8186. (b) Jo, M.; Seo, J.; Lindoy, L. F.; Lee,
S. S. Dalton Trans. 2009, 6096. (c) Yoon, I.; Seo, J.; Lee, J.-E.; Song, M. R.; Lee,
S. Y.; Choi, K. S.; Jung, O.-S.; Park, K.-M.; Lee, S. S. Dalton Trans. 2005, 2352.
r
pubs.acs.org/IC
Published on Web 07/20/2010
2010 American Chemical Society

Article
Inorganic Chemistry, Vol. 49, No. 16, 2010 7511
Chart 1. Oxathia- and Azaoxathia-Macrocycles L1-L4 Used in
This Work
128.1, 127.7, 121.3, 111.8, 70.5, 70.4, 30.9, 30.0. Mass spectrum
m/z (EI): 452.7 (L1)þ.
Synthesis and Characterization of L2. The synthetic procedure
employed was almost the same as that for macrocycle L1 except
for the use of 11b as the dichloride. Flash column chromato-
graphy (SiO2, n-hexane: ethyl acetate/9:1) afforded the product
as a white solid in 40% yield. Mp: 125-126 °C. IR (KBr pellet):
3090, 3043, 2929, 2891, 2360, 2329, 1598, 1583, 1491, 1245, 1098,
754 cm-1. Anal. Calcd for [C25H27NO3S2]: C, 66.20; H, 6.00; N,
3.09. Found: C, 66.17; H, 6.11; N, 2.90%. 1H NMR (300 MHz,
CDCl3): δ 7.86-6.94 (m, 11H, aromatic), 5.14 (s, 4H, ArCH2O),
3.76 (s, 4H, ArCH2S), 3.14 (t, 4H, OCH2CH2), 2.40 (t, 4H,
CH2CH2S). 13C NMR (75 MHz, CDCl3) 156.5, 156.2, 137.6,
130.9, 128.5, 127.9, 122.7, 121.8, 112.2, 71.9, 70.1, 30.3, 29.4.
Mass spectrum m/z (ESI): 454.5 (L2 þ 1)þ.
Synthesis and Characterization of L3. The synthetic procedure
employed was almost the same as that for macrocycle L1, except
for the use of 2-mercaptoethyl sulfide as the dithiol. Flash col-
umn chromatography (SiO2, n-hexane: ethyl acetate/9:1) affor-
ded the product as a white solid in 48% yield. Mp: 101-102 °C.
IR (KBr pellet): 3056, 3023, 2930, 2891, 2869, 1594, 1492, 1450,
1236, 1013, 755 cm-1. Anal. Calcd for [C26H28O2S3]: C, 66.63;
H, 6.02. Found: C, 66.43; H, 6.02%. 1H NMR (300 MHz,
CDCl3): δ 7.69-6.94 (m, 12H, aromatic), 5.04 (s, 4H, ArCH2O),
3.78 (s, 4H, ArCH2S), 2.50, 2.47 (m, overlapped, 8H, SCH2-
CH2S). 13C NMR (75 MHz, CDCl3): 156.6, 137.3, 130.8, 128.8,
128.5, 128.2, 128.2, 127.6, 121.5, 112.1, 70.6, 32.4, 32.0, 29.9.
Mass spectrum m/z (EI): 468 (L4)þ.
Synthesis and Characterization of L4. The synthetic procedure
was almost the same as that for L1 except for the use of
2,20-(ethylenedioxy)diethanethiol as the dithiol. Flash column
chromatography (SiO2; n-hexane-ethyl acetate 1:9) afforded the
product as a white solid in 41% yield. Mp: 79-80 °C. IR (KBr
pellet): 3042, 3011, 2932, 2892, 1705, 1591, 1474, 1451, 1224,
1107, 749, 703 cm-1. Anal. Calcd for [C32H39O6S2]: C, 65.84; H,
6.73. Found: C, 65.79; H, 6.43%. 1H NMR (300 MHz, CDCl3):
δ 7.65-6.90 (m, 12H, aromatic), 5.09 (s, 4H, ArCH2O), 3.85
(s, 4H, ArCH2S), 3.49 (t, 4H, OCH2CH2S), 3.37 (s, 4H,
OCH2CH2O), 2.61 (t, 4H, CH2CH2S). 13C NMR (75 MHz,
CDCl3): 156.5, 137.6, 130.7, 128.7, 128.3, 127.8, 127.2, 126.8,
121.2, 111.9, 70.9, 70.2, 31.1 30.3. Mass spectrum m/z (EI): 496
(L4)þ.
The continuing interest in metallosupramolecular assem-
blies incorporating thiamacrocyclic systems and the limited
research in the area so far has prompted us to investigate the
possibility of fabricating new structures of this type. In parti-
cular, we were interested in extending the area using some
larger thiamacrocycle system with a rigid conformation by
employing three aromatic units. Accordingly, the new series
of tribenzo-thiaoxa(aza)-macrocycles (L1-L4, Chart 1) was
synthesized, and their complexes with silver(I) perchlorate,
tetrafluoroborate, and nitrate as well as with copper(I) iodide
were prepared and characterized.
Experimental Section
General. All chemicals and solvents used in the syntheses were
of reagent grade and were used without further purifica-
tion. NMR spectra were recorded on a Bruker 300 spectrometer
(300 MHz). FT-IR spectra were measured with a VERTEX 80v
FT-IR spectrometer. The mass spectra were obtained on a
JEOL JMS-700 spectrometer (FAB) and an Applied Biosystems
3200 Q-TRAP (ESI). The elemental analysis was carried out on
a LECO CHNS-932 elemental analyzer.
Preparation of 1, [Ag(L1)(ClO4)]n. Silver perchlorate (4.58 mg,
0.022 mmol) in methanol (2 mL) was added to a solution of L1
(10.0 mg, 0.022 mmol) indichloromethane (2 mL). A fine powder,
which precipitated from the solution, was filtered off. Vapor
diffusion of diethyl ether into the DMF solution gave colorless
crystalline product 1 suitable for X-ray analysis (yield: 48%).
Mp: 213-215 °C. IR (KBr, pellet): 2925, 2874, 2868, 1599, 1495,
1244, 1107 (ClO4-), 1023, 468, 621 cm-1. Anal. Calcd for [C26H30-
AgClO8 S2]: C, 46.06; H, 4.46; S, 9.46. Found: C, 46.56; H, 4.30; S,
9.47%. Mass spectrum m/z (ESI): 561.5 [Ag(L1)]þ.
Caution! The respective perchlorate-containing complexes are
potentially explosive, and appropriate precautions should be taken
during their preparation, handling, and storage.
Synthesis and Characterization of L1. Cesium carbonate (4.21 g,
13.0 mmol) was dissolved in DMF (1000 mL) in a 3 L round-
bottom flask. 2-Mercaptoethyl ether (Aldrich, 0.86 g, 6.22 mmol)
and dichloride 11a (2.00 g, 5.20 mmol) were dissolved in DMF
(30 mL) and placed in a 50 mL glass syringe. The contents of the
syringe were added dropwise at a regular rate (0.6 mL h-1) into
the DMF solution under a nitrogen atmosphere with the aid of a
microprocessor controlled syringe pump at 45-50 °C over 50 h.
The mixture was allowed to stand for a further 10 h. After
cooling to room temperature, the reaction mixture was filtered
and the solvent evaporated. Water (100 mL) was added, and the
mixture was extracted with dichloromethane. The organic phase
was dried over anhydrous sodium sulfate and filtered, and the
solvent was removed to give a yellow oil. Flash column chro-
matography (SiO2, n-hexane: ethyl acetate/9:1) afforded the
product as a white solid in 57% yield. Mp: 90-92 °C. IR
(KBr pellet): 3063, 2927, 2913, 2867, 1597, 1492, 1452, 1234,
1096, 751 cm-1. Anal. Calcd for [C26H28O3S2]: C, 68.99; H, 6.24.
Preparation of 2, [Ag(L2)]ClO4 CH3OH. Silver perchlo-
3
rate (9.14 mg, 0.044 mmol) in methanol (2 mL) was added to
L2 (20.0 mg, 0.044 mmol) in dichloromethane (2 mL). The white
precipitate that formed was separated and dissolved in aceto-
nitrile. Slow evaporation of the acetonitrile solution afforded
crystalline 2 suitable for X-ray analysis (yield: 60%). Mp:
233-234 °C (decomp.). IR (KBr pellet): 3076, 2991, 2940,
2855, 2363, 1703, 1696, 1603, 1490, 1457, 1225, 1108 (ClO4-),
1051, 757, 622 cm-1. Anal. Calcd for [C26H29AgCl3NO7S2]: C,
41.87; H, 3.92; N, 1.88. Found: C, 41.68; H, 3.67; N, 1.96%.
Mass spectrum m/z (ESI): 560.5 [Ag(L2)]þ.
Preparation of 3, {[Ag2(L2)(CH3OH)](BF4)2}n. Silver tetra-
fluoroborate (8.60 mg, 0.044 mmol) in methanol (2 mL) was
added to a solution of L2 (20.0 mg, 0.044 mmol) in dichloro-
methane (2 mL). Slow evaporation of the solution afforded
colorless crystalline 3 that proved suitable for X-ray analysis
(yield: 52%). Mp: 200-201 °C (decomp.). IR (KBr pellet): 3050,
1
Found: C, 68.87; H, 5.94%. H NMR (300 MHz, CDCl3): δ
7.70-6.91 (m, 12H, aromatic), 5.02 (s, 4H, ArCH2O), 3.79 (s,
4H, ArCH2S), 3.33 (t, 4H, CH2CH2O), 2.51 (t, 4H, CH2CH2S).
13C NMR (75 MHz, CDCl3) 156.5, 137.3, 130.7, 128.7, 128.2,

7512 Inorganic Chemistry, Vol. 49, No. 16, 2010
Kang et al.
Table 1. Crystal and Experimental Data for L1, L2, L3, and 1-7
L1
L2
L3
C26H28O2S3
468.66
1
2
formula
fw
temp
C26H26O3S2
452.60
296(2)
C25H27NO3S2
453.60
296(2)
C26 H27AgClO7S2
658.92
296(2)
C26H31AgClNO8S2
692.96
173(2)
173(2)
triclinic
P1
cryst syst
space group
Z
monoclinic
P21/c
monoclinic
P21/n
monoclinic
P21/c
monoclinic
P21/n
4
4
2
4
4
˚
a (A)
8.5743(7)
8.7776(7)
30.463(2)
90
8.6987(5)
8.9216(5)
28.6653(15)
90
8.1947(9)
8.2259(10)
18.386(2)
95.482(2)
91.689(2)
104.032(2)
1195.1(2)
1.302
9.0357(11)
16.609(2)
17.374(2)
90
13.5485(12)
10.9249(9)
18.8859(16)
90
˚
b (A)
˚
c (A)
R (deg)
β (deg)
γ (deg)
97.707(4)
90
94.184(3)
90
95.371(6)
90
90.142(2)
90
3
˚
V (A )
D
2272.0(3)
1.323
0.260
2218.7(2)
1.358
0.268
2595.9(6)
1.686
1.086
2795.4(4)
1.647
1.016
calc (g/cm3)
absorption coefficient
0.331
(mm-1
cryst size (mm3)
)
0.40 ꢀ 0.30 ꢀ 0.20
0.22 ꢀ 0.16 ꢀ 0.02
0.24 ꢀ 0.20 ꢀ 0.15
0.13 ꢀ 0.06 ꢀ 0.02
0.20 ꢀ 0.10 ꢀ 0.08
52.00
2θmax (deg)
max. and min transmission 0.9498 and 0.9031
51.98
56.20
53.00
55.48
0.9231 and 0.8226
0.0861
0.1903
R
wR
0.0387
0.1024
0.0488
0.1221
0.0649
0.1692
0.0364
0.0933
no. of reflections used
[>2 σ(I)]
4467 [R(int) = 0.0363] 5405 [R(int) = 0.1420] 4840 [R(int) = 0.0593] 6028 [R(int) = 0.0529] 5488 [R(int) = 0.0667]
diffractometer
structure determination
refinement
Bruker APEX-II CCD
SHELXTL
full-matrix
Bruker SMART CCD
SHELXTL
full-matrix
Bruker SMART CCD
SHELXTL
full-matrix
Bruker APEX-II CCD
SHELXTL
full-matrix
Bruker SMART CCD
SHELXTL
full-matrix
3
4
5
6
7
formula
fw
temp
C
875.00
26H31Ag2B2F8NO4S2 C24H22.40Ag0.80N2.40O4S2.40 C26.50H29ClCuIO3S2
C27H30Cl2CuIO2S3
744.03
100(2)
C57H66Cl2Cu4I4O8S4
1840.00
152(2)
571.68
173(2)
monoclinic
P21/c
685.51
164(2)
173(2)
monoclinic
P21/c
cryst syst
space group
Z
triclinic
P1
orthorhombic
Pna21
triclinic
P1
4
5
4
4
2
˚
a (A)
11.1076(3)
14.0306(5)
19.8652(6)
90
17.2650(7)
22.7228(9)
8.2636(3)
90
10.6591(5)
13.2940(7)
20.8899(10)
73.689(2)
76.230(2)
72.909(2)
2676.3(2)
1.701
20.870(4)
6.8790(14)
20.667(4)
90
13.5704(14)
15.2959(18)
18.728(2)
70.101(6)
69.167(6)
65.368(6)
3217.1(6)
1.899
˚
b (A)
˚
c (A)
R (deg)
β (deg)
γ (deg)
100.7290(10)
90
103.506(2)
90
90
90
3
˚
V (A )
D
3041.80(16)
1.911
3152.2(2)
1.506
0.881
2967.1(10)
1.666
2.192
calc (g/cm3)
absorption coefficient 1.509
(mm-1
2.253
3.486
)
cryst size (mm3)
2θmax (deg)
max. and min
transmission
R
0.27 ꢀ 0.10 ꢀ 0.06
56.66
0.9149 and 0.6861
0.17 ꢀ 0.15 ꢀ 0.09
63.98
0.7463 and 0.6270
0.28 ꢀ 0.20 ꢀ 0.10
55.26
0.8061 and 0.5711
0.05 ꢀ 0.04 ꢀ 0.01
53.00
0.9784 and 0.8983
0.38 ꢀ 0.15 ꢀ 0.09
52.00
0.7560 and 0.3509
0.0256
0.0686
7554 [R(int) = 0.0221] 10560 [R(int) = 0.2300]
0.0603
0.1474
0.0347
0.0933
12296 [R(int) = 0.0428] 3411 [R(int) = 0.0451]
0.0415
0.1103
0.1075
0.2843
12616 [R(int) = 0.0468]
wR
no. of reflections
used [>2σ(I)]
diffractometer
structure
Bruker APEX-II CCD Bruker APEX-II CCD
SHELXTL
full-matrix
Bruker APEX-II CCD
SHELXTL
6BX Bruker Proteum 300 Bruker APEX-II CCD
SHELXTL
SHELXTL
full-matrix
SHELXTL
determination
refinement
full-matrix
full-matrix
full-matrix
2981, 2955, 2886, 2349, 1702, 1493, 1308, 1091, 1055 (BF4-),
1040, 777 cm-1. Anal. Calcd for [C26H31AgClBF4NO4S2]: C,
41.57; H, 4.16; N, 1.86. Found: C, 41.90; H, 3.85; N, 1.92%.
Mass spectrum m/z (ESI): 561.5 [Ag(L2)]þ.
1046, 1007, 753 cm-1. Anal. Calcd for [C27H30AgBF4N2O3S2]:
C, 48.03; H, 4.46; S, 13.74. Found: C, 48.25; H, 4.22; S, 14.19%.
Mass spectrum m/z (FAB): 1214.19 [Ag2(L3)2(NO3)]þ.
Preparation of 5, [Cu2I2(L1)2] CH2Cl2. A dichloromethane
3
Preparation of 4, [Ag2(L3)2(NO3)2] 2CH3CN. Silver nitrate
(2 mL) solution of L1 (20.0 mg, 0.044 mmol) was allowed to
diffuse slowly into an acetonitrile (2 mL) solution of CuI (8.42
mg, 0.044 mmol) in a capillary tube (i.d. 5 mm). Slow evapora-
tion of the solution gave colorless crystalline 5 that proved
suitable for X-ray analysis (yield: 62%). Mp: 177-178 °C
(decomp.). IR (KBr pellet): 3063, 3034, 2921, 2855, 1597,
1492, 1448, 1386, 1286, 1243, 1153, 1117, 1047, 1021, 763, 733
cm-1. Anal. Calcd for [C26H30CuIO4S2]: C, 47.24; H, 4.57; S,
3
(7.25 mg, 0.043 mmol) in methanol (2 mL) was added to L3
(20 mg, 0.043 mmol) in dichloromethane (2 mL). The colorless
precipitate obtained was separated and dissolved in acetonitrile.
Slow evaporation of the acetonitrile solution gave crystalline 4
that proved suitable for X-ray analysis (yield: 42%). Mp:
110-111 °C (decomp.). IR (KBr pellet): 3051, 3032, 2920,
2869, 2359, 2340, 1598, 1492, 1453, 1383 (NO3-), 1241, 1099,

Article
Inorganic Chemistry, Vol. 49, No. 16, 2010 7513
Scheme 1. Synthesis of the Macrocyclic Ligands L1-L4
Figure 1. Crystal structures of (a) L1, (b) L2, and (c) L3. Selected torsion
angles (deg) between two adjacent donor atoms: for L1, S1-C-C-O2 =
-151.11(63), O2-C-C-S2 = -162.34(41); for L2, S1-C-C-O2 =
-68.36(21), O2-C-C-S2 = -68.95(20); for L3, S1-C-C-S2 =
-174.83(22), S2-C-C-S3 = 174.17(32).
9.70. Found: C, 46.98; H, 4.75; S, 9.99%. Mass spectrum m/z
(ESI): 515.5 [Cu(L1)]þ.
Preparation of 6, [CuI(L3)] CH2Cl2. A dichloromethane (2 mL)
3
solution of L3 (10.0mg, 0.021 mmol) was allowed to diffuse slowly
into a methanol (2 mL) solution of CuI (4.1 mg, 0.021 mmol) in a
capillary tube (i.d. 5 mm). Slow evaporation of the solution gave
the colorless crystalline 6 that proved suitable for X-ray analysis
(yield: 36%). Mp: 200-201 °C (decomp.). IR (KBr pellet): 3034,
2985, 2918, 2870, 2856, 2353, 2330, 1699, 1597, 1489, 1452, 1403,
1288, 1240, 1099, 1043, 1011, 841, 7490 cm-1. HRMS (FAB)
Calcd for C26H28CuO2S3 [Cu(L3)]þ: 531.0547. Found: 531.0574.
11 were prepared from the corresponding dialdehydes 9
and dialcohols 10 using a known procedure.9 L1-L4 were
commonly obtained by coupling macrocyclization reac-
tions between 11 and the corresponding dithiols in the
presence of Cs2CO3 under high dilution conditions; again
reasonable yields were obtained (L1, 57%; L2, 40%; L3,
1
48%; L4, 41%). The H and 13C NMR spectra together
Preparation of 7, {[Cu4I4(L4)2] CH2Cl2}n. A dichloromethane
3
(2 mL) solution of L4 (20.0 mg, 0.040 mmol) was allowed to dif-
fuse slowly into an acetonitrile (2 mL) solution of CuI (7.67 mg,
0.040 mmol) in a capillary tube (i.d. 5 mm). Slow evaporation of
the solution gave colorless crystalline 7 that proved suitable for
X-ray analysis (yield: 65%). Mp: 206-208 °C. IR (KBr pellet):
3061, 3033, 2918, 2859, 2358, 2340, 1599, 1495, 1453, 1239, 1102,
1048, 1015, 753, 696, 585 cm-1. HRMS (FAB) Calcd for C28H32-
CuO4S2 [Cu(L4)]þ: 559.1038. Found: 559.1055.
with elemental analysis and mass spectra were all in clear
agreement with the proposed structures.
The structures of three of the new macrocycles were
also characterized in the solid state by single-crystal X-ray
crystallography (Figure 1). Colorless crystals of L1, L2,
and L3 suitable for X-ray analysis were obtained by slow
evaporation from the solutions of dichloromethane (L1
and L3) and methanol (L2). In each structure, the oxygen
atoms adjacent to the center aromatic ring are oriented in
an endodentate fashion, while all sulfur atoms are orien-
tated exodentately. L1 and L3 have relatively nonfolded
configurations in which both of their exodentate sulfur
donors are widely separated due to the aliphatic segments
between the two adjacent donors being associated with
anti arrangements with the torsion angles [for L1,
-151.11(63) and -162.34(41)°; for L3, -174.83(22) and
174.17(32)]. In L2, however, the two adjacent donors are
associated with gauche arrangements with the torsion
angles [-68.36(21) and -68.95(20)]. Accordingly, the
X-Ray Crystallographic Analysis. All diffraction data, except
that for 6, were measured at 173 K on a Bruker SMART CCD
diffractometer equipped with graphite monochromated Mo KR
˚
radiation (λ = 0.71073 A). The cell parameters for the com-
pounds were obtained from a least-squares refinement of the
spot (from 45 collected frames) using the SMART program. The
intensity data were processed using the Saint Plus program. All
of the calculations for the structure determination were carried
out using the SHELXTL package (version 6.22).6 Absorption
corrections were applied using XPREP and SADABS.7 Com-
pound 7 shows the relatively high values of R and wR because of
the disorders for S4 and C48 atoms. Crystal data for L1, L2, L3,
and 1-7 are given in Table 1.
The diffraction data for 6 were measured at 100 K with syn-
chrotron radiation on a 6BX Bruker Proteum 300 CCD detec-
tor with a platinum-coated double-crystal monochromator at
the Pohang Accelerator Laboratory, Korea. The HKL2000
(v. 0.98.694) software package8 was used for data collection, cell
refinement, reduction, and absorption correction. Collected data
were corrected for absorbance using SADABS on the basis of Laue
symmetry using equivalent reflections.
respective S S distances in the macrocycles are
3 3 3
1
7.649(9) A for L , 6.302(8) A for L , and 8.047(18) A
2
˚
˚
˚
for L3.
Preparation and Structures of the Silver(I) Complexes
(1-4). On complexation with silver(I) salts (perchlorate,
nitrate, and tetrafluoroborate), four new supramolecular
complexes (1-4) were obtained for L1-L3 as depicted in
Scheme 2. The preparation of the corresponding silver(I)
complexes with L4 was not possible.
Results and Discussion
Reaction of silver perchlorate with L1 in methanol/
dichloromethane yielded a colorless precipitate. Vapor
diffusion of diethyl ether into the DMF solution of the
complex gave crystalline 1. X-ray analysis (Figure 2) of 1
revealed it to have the formula [Ag(L1)(ClO4)]n. Selected
geometric parameters are presented in Table 2. Interest-
ingly, 1 is an exocoordinated 1-D polymeric species, and
Syntheses and Characterization of Macrocyclic Ligands
L1-L4. Synthesis of the target macrocycles involved four
steps starting from ditosylates 8 (Scheme 1), with each
step proceeding smoothly in reasonable yield. Dichlorides
(6) Sheldrick, G. M. SHELXTL-PC, version 6.22; Bruker-Analytical X-ray
Services: Madison, WI, 2001.
(7) Sheldrick, G. M. SADABS; University of Gottingen: Gottingen,
Germany, 2000.
€
€
(8) Otwinowski, Z.; Minor, W. In Methods in Enzymology; Carter, C. W.,
Jr., Sweet, R. M., Eds.; Academic Press: New York, 1997; Vol. 276, part A,
pp 307-326.
(9) (a) Sultana, K. F.; Lee, S. Y.; Lee, J. Y.; Park, K.-M.; Lee, S. S. Bull.
Korean Chem. Soc. 2008, 29, 241. (b) Sultana, K. F.; Lee, S. Y.; Lee, J.-E.; Seo,
J.; Lee, S. S. Inorg. Chem. Commun. 2007, 10, 1496.

7514 Inorganic Chemistry, Vol. 49, No. 16, 2010
Kang et al.
Scheme 2. The Silver(I) Complexes Synthesized in This Study
Figure 2. Exocyclic 1-D polymeric structure of 1, [Ag(L1)(ClO4)]n:
(a) coordination sphere and (b) 1-D network.
˚
Table 2. Selected Bond Lengths (A), Bond Angles (deg), and Torsion Angles
(deg) for 1a
Ag1-S1
Ag1-O2
2.487(8)
Ag1-S2
2.486(8)
2.560(3)
5.595(21)
2.710(23) Ag1-C3A
2.620(26) Ag1 O1
5.422(20)
its asymmetric unit contains one L, one Ag atom, and one
ClO4-. Each Ag atom, which lies outside the cavity, is
bonded to one O and two S atoms of one macrocycle as
well as one aryl carbon atom (C3) from an adjacent L1,
resulting in a -L1-Agþ-L1-Agþ- type 1-D polymeric
Ag1 O4
Ag1 O3
3 3 3
3 3 3
3 3 3
S1-Ag1-S2
129.35(3)
S1-Ag1-O2
S1-Ag1-C3A
S2-Ag1-O2
O2-Ag1-O4
74.50 (5)
109.94(7)
76.35 (6)
157.96 (8)
S1-Ag1-O4
85.52 (7)
118.29(7)
110.96 (6)
66.32(30)
S2-Ag1-C3A
S2-Ag1-O4
˚
chain (Figure 2b). The Ag1-C3 distance [2.560(3) A] lies
S1-C18-C17-O2
O2-C16-C15-S2 -54.69(35)
10
˚
within the limits (2.47-2.77 A) reported for such a π bond.
The coordination sphere is completed by an O atom from
a Symmetry operation (A): x, -y þ 3/2, z þ 1/2.
-
ClO4 bound in a monodentate manner with a bond
˚
length [Ag1-O4, 2.620(26) A] that falls within the range
observed for other monodentate perchlorate complexes
of silver.4b,10d,11 Thus, the Ag atom is effectively five-
coordinate with the coordination geometry best described
as a distorted trigonal bipyramid. The S2C donor atoms
define an equatorial trigonal plane [S1-Ag1-C3, 109.94(7);
C3-Ag1-S2, 118.29(7); S1-Ag1-S2, 129.35(3)] around
the central silver, with axial positions occupied by one
ether O atom (O2) and another O atom (O4) from the
monodentate ClO4- [<O 2 -Ag1-O4, 158.0(8)°]. The Ag
˚
atom is defected out of the trigonal plane by 0.224 A
toward O4. The two oxygen donors (O1 and O3) lying
between the aromatic units remain uncoordinated
˚
[Ag1 O1, 5.595(21); Ag1 O3, 5.422(20) A]. It is also
Figure 3. Endocyclic structure of 2, [Ag(L2)]ClO4 CH3OH. The
noncoordinating solvent molecule is omitted for clarity.
3 3 3
3 3 3
3
noteworthy that the large conformational change in the
ligand upon complexation is caused by altering the tor-
sion angles between two adjacent donors, changing from
the anti [-151.11(63) and -162.34(41)°] to the gauche
form [66.32(30) and -54.69(35)°].
The reaction of silver perchlorate with L2 in methanol/
dichloromethane yielded a colorless precipitate which
was recrystallized from acetonitrile to give crystalline 2.
X-ray analysis of 2 (Figure 3) revealed it to have the
formula [Ag(L2)]ClO4. The selected geometric parameters
are presented in Table 3. In marked contrast to the metal
ion position in 1 (derived from L1), 2 is a typical endo-
cyclic mononuclear complex in which the silver(I) ion
has a three-coordinate, trigonal planar geometry with the
silver being bound to the two sulfur and one nitrogen
(10) (a) Lee, S. Y.; Jung, J. H.; Vittal, J. J.; Lee, S. S. Cryst. Growth Des.
2010, 10, 1033. (b) Liddle, B. J.; Hall, D.; Lindeman, S. V.; Smith, M. D.;
Gardinier, J. R. Inorg. Chem. 2009, 48, 8404. (c) Zheng, X.-F.; Zhu, L.-G. Cryst.
Growth Des. 2009, 9, 4407. (d) Kim, H. J.; Lee, S. S. Inorg. Chem. 2008, 47,
10807. (e) Lee, J.-E.; Lee, J. Y.; Seo, J.; Lee, S. Y.; Kim, H. J.; Park, S. H.; Park,
K.-M.; Lindoy, L. F.; Lee, S. S. Polyhedron 2008, 27, 3004. (f) Lee, J. Y.; Lee,
S. Y.; Seo, J.; Park, C. S.; Go, J. N.; Sim, W.; Lee, S. S. Inorg. Chem. 2007, 46,
6221. (g) Kim, H. J.; Yoon, I.; Lee, S. Y.; Seo, J.; Lee, S. S. Tetrahedron Lett.
2007, 48, 8464. (h) Munakata, M.; Wu, L. P.; Ning, G. L.; Kuroda-Sowa, T.;
Meakawa, M.; Suensga, Y.; Maeno, N. J. Am. Chem. Soc. 1999, 121, 4968.
(11) Jung, O.-S.; Lee, Y.-A.; Kim, Y. J.; Hong, J. Cryst. Growth Des. 2002,
2, 497.

Article
Inorganic Chemistry, Vol. 49, No. 16, 2010 7515
˚
Table 3. Selected Bond Lengths (A), Bond Angles (deg), and Torsion Angles
(deg) for 2
Ag1-N1
Ag1-S2
2.406(6)
2.530(2)
2.962(64) Ag1 O3
Ag1-S1
Ag1 O1
2.596(3)
3.008(59)
2.950(60)
118.80(15)
3 3 3
Ag1 O2
N1-Ag1-S1
S1-Ag1-S2
3 3 3
3 3 3
101.58(15)
139.10(8)
N1-Ag1-S2
S1-C17-C16-O2 -68.70(10)
O2-C15-C14-S2
70.88(80)
donor atom of L2. As might be expected, the pyridine N
atom in L2 appears to bind strongly to the silver center
˚
[Ag1-N1, 2.406(6) A]. The Ag-S bond distances in 2
˚
[Ag1-S1, 2.596(3), Ag1-S2, 2.530(2) A] are typical but
slightly longer than those in 1 (average 2.49 A). Thus,
˚
since 2 shows strong Ag-N(pyridine) bonding, this may
contribute to slightly weaker Ag-S bonds in this complex
if bond length is taken to be a measure of bond strength.
Unlike the coordination of perchlorate in 1, the perchlo-
rate ion in 2 remains uncoordinated; the preferred anion-
free mononuclear endocyclization in 2 presumably re-
flects the overall strong coordination of the donor set
(including, as mentioned above, the pyridine nitrogen
atom) of L2. Additional interactions between the Ag atom
and O donors (dashed lines in Figure 3), which are shorter
than the sum of the van der Waals radii of Ag and O (3.20
Figure 4. Endo/exocyclic 1-D polymeric structure of 3, {[Ag2(L2)-
(CH3OH)](BF4)2}n: (a) asymmetric unit, (b) side view, and (c) 1-D net-
work. The anions are omitted, except in b.
˚
Table 4. Selected Bond Lengths (A), Bond Angles (deg), and Torsion Angles
(deg) for 3a
˚
A), are also present; three ether oxygens [Ag1 O1,
3 3 3
Ag1-N1
Ag1-S2
Ag2-S1A
2.337(17) Ag1-S1
2.602(5)
2.536(6)
2.350(2)
3.137(16)
2.898(16)
2.813(18)
3.008(6); Ag1 O2, 2.962(6); and Ag1 O3, 2.950(6)
˚
A] and one perchlorate oxygen [Ag1 O4, 2.931(11),
3 3 3
3 3 3
3 3 3
2.568(5)
2.506(5)
2.935(15) Ag1 O2
Ag2-S2
Ag2-O4
Ag1 O1
Supporting Information] interact weakly with the silver.
As mentioned, a comparison of the different coordina-
tion modes adopted in 1 and 2 supported the idea that the
existence of pyridine as a strong coordinating site in L2
relative to the presence of an aryl group in L1 can be a
controlling factor influencing exo- (for 1) versus endo-
coordination (for 2) behavior. The preferred endocoordi-
nation mode of 2 appears likely to reflect the presence of
the strongly bound pyridine unit in L2, which might be
expected to promote the formation of the observed dis-
crete 1:1 species. In contrast, L1 has no pyridine unit, and
instead the π coordination of silver(I) with an the adjacent
aryl group occurs, giving rise to the formation of a 1-D
network species.
3 3 3
3 3 3
Ag1 O3
2.772(15) Ag1 F3
2.803(15) Ag2 F6
3 3 3
3 3 3
Ag2-F2
3 3 3
N1-Ag1-S1
S1-Ag1-S2
S1A-Ag2-S2
S1-C14-C15-O2
106.96(4)
N1-Ag1-S2
122.95(4)
129.61(17)
119.88(17)
68.06(21)
S2-Ag2-O4
S1A-Ag2-O4
O2-C16-C17-S2
128.09(6)
111.14(7)
55.03(22)
a Symmetry operation (A): -x þ 1, y þ 1/2, -z þ 1/2.
in the range 107.0-130.0° for Ag1 and 111.1-128.1° for
Ag2.
Complex 3 is a rare example of a 1-D coordination
polymer incorporating both endo- and exocyclic metal
ion coordination, with the first example of this type also
being reported by us.12 The formation of such a 1-D
network seems to be a consequence of the stabilization of
the exocyclic Ag2 coordination sphere relative to that
of Ag1. Comparing the bond distances for the endo-
and exocyclic silver atoms, it is noteworthy that the
Ag-S distances for the exocyclic Ag2 atom [Ag2-S1A,
Reaction of silver tetrafluoroborate with L2 in methanol/
dichloromethene afforded colorless crystalline 3 that was
suitable for X-ray analysis. Very interestingly, the crys-
tal structure of 3 (Figure 4; Table 4) shows an unusual
1-D arrangement, with the formula being {[Ag2(L2)-
(CH3OH)](BF4)2}n. In this structure, successive endocyc-
lic silver(I) complex units are linked with exocyclic silver-
(I) units via Ag-S bonds, resulting in the observed 1-D
network. Selected geometric parameters are presented in
Table 3. Similar to the mononuclear endocoordination
observed in 2, the endocyclic Ag1 atom in 3 is bonded to a
NS2 donor set from L2 in a twisted conformation [S2-
C-C-O1, -68.36(21); O1-C-C-S1, -68.95(20)]; three
ether oxygens from the macrocycle also interact weakly
with silver: Ag1 O1, 2.935(15); Ag1 O2, 3.137(16);
˚
2.506(5); Ag2-S2, 2.536(6) A] are shorter than those for
the endocyclic Ag1 atom [Ag1-S1, 2.602(5); Ag1-S2,
2.568(5) A]. Furthermore, the Ag2 atom shows additional
˚
interactions to two adjacent BF4- ions (Ag2 F, 2.803
3 3 3
˚
and 2.813 A). Overall, it seems clear that synergic con-
tributions from the ligand, solvent, and anion all con-
tribute toward the stabilization of the observed unique
endo/exocyclic coordination behavior of the silver atoms
in 3.
Reaction of silver nitrate with L3 in methanol/dichloro-
methane yielded a colorless precipitate. Slow evaporation
3 3 3
3 3 3
˚
and Ag1 O3, 2.772(15) A. The Ag2 atom outside the
3 3 3
cavity bridges the endocyclic Ag1 coordination spheres,
resulting in a [Ag2(L1)(CH3OH)]þ repeating unit that
repeats via Ag-S bonds. The coordination sphere of
Ag2 is completed by a methanol molecule. Accordingly,
the local coordination geometry of each Ag atom is dis-
torted trigonal planar, with the “trigonal” angles falling
(12) (a) Lee, J. Y.; Lee, S. Y.; Park, S.; Kwon, J.; Sim, W.; Lee, S. S. Inorg.
Chem. 2009, 48, 8934. (b) Lee, J. Y.; Kim, H. J.; Jung, J. H.; Sim, W.; Lee, S. S.
J. Am. Chem. Soc. 2008, 130, 13838. (c) Yoon, I.; Seo, J.; Lee, J.-E.; Park, K.-M.;
Kim, J. S.; Soo, M.; Lah, M.; Lee, S. S. Inorg. Chem. 2006, 45, 3487. (d) Heller,
€
M.; Sheldrick, W. S. Z. Anorg. Allg. Chem. 2003, 629, 1589. (e) Rottgers, T.;
Sheldrick, W. S. Z. Anorg. Allg. Chem. 2001, 627, 1976.

7516 Inorganic Chemistry, Vol. 49, No. 16, 2010
Kang et al.
of an acetonitrile solution of this product gave crystals
of 4. The X-ray analysis revealed that 4 is a discrete
one Ag atom, one coordinated nitrate ion, and one CH3CN
molecule. The structural unit in Figure 5 is generated
through an inversion symmetry. The structure consists of
a dimeric arrangement in which two macrocycles are
sandwiching two silver(I) ions. Each four-coordinated
Ag atom lies outside the macrocyclic cavity and is bonded
to two S atoms from one L3 and one S atom from a
different L3. The coordination environment of each silver
in 4 is completed by an additional bond to a monodentate
nitrato ligand. The “tetrahedral” bond angles around the
Ag atom vary from 80.9(7) (O3-Ag1-S3A) to 137.6(3)°
(S2-Ag1-S3A). These large deviations of the angles
from the regular tetrahedron are due to the formation
of the pentagonal rings [Ag1-S2-C-C-S1] via Ag-S
bonds together with the steric hindrance between two
adjacent ligands linked with a Ag atom. The separation of
cyclic dimer of formula [Ag2(L3)2(NO3)2] 2CH3CN (see
Figure 5). The selected geometric parameters are pre-
3
sented in Table 5. The asymmetric unit contains one L3,
˚
the two Ag atoms (Ag1 Ag1A, 6.075 A) is far outside
3 3 3
the range expected for an agentophilic interaction. The
FAB mass spectrum of 4 contains a peak at m/z 1214,
which corresponds to [Ag2(L3)2(NO3)]þ as [M-NO3-
2CH3CN]þ; the peak pattern is in agreement with the
calculated isotopic pattern for this ion (Figure 6).
NMR Titration Study of Silver(I) Complexation. As
shown in Figures 2 and 3, the two different silver(I) com-
plex structures found for 1 and 2 clearly reflect the
different coordination behaviors of the respective macro-
cycles, reflecting the presence of the benzo (L1) and pyr-
idine (L2) subunits. 1H NMR titrations for each silver(I)
system were performed in CD3CN/CDCl3 (1:1) in order
to explore the complexation behavior in solution (and
also for comparison with the solid state behavior), The
signals for the four methylene (H1-4) and the aromatic
(Ha-f) protons in L1 and L2 were well resolved and readily
identified (Figures 7a and 8a). Upon stepwise addition of
AgClO4 (0-1.5 equiv) to each ligand solution, the signals
for all aliphatic protons shifted downfield, in keeping
with the occurrence of silver(I) complex formation, with
the ligand exchange rate being fast on the NMR time
scale.
Figure 5. Cyclic dimer structure of 4, [Ag2(L3)2(NO3)2] 2CH3CN: (a)
front view and (b) side view. The noncoordinating solvent molecules are
omitted.
3
˚
Table 5. Selected Bond Lengths (A), Bond Angles (deg), and Torsion Angles
(deg) for 4a
Ag1-S1
2.654(7) Ag1-S2
2.497(3) Ag1-S3A
2.542(8)
2.545(8)
109.70(7)
137.64(3)
Ag1-O3
S1-Ag1-S2
S1-Ag1-S3A
O3-Ag1-S3A
86.00(2)
115.80(2)
80.93(7)
S1-Ag1-O3
S2-Ag1-S3A
S1-C25-C24-S2 -65.50(27) S2-C23-C22-S3 -179.93(15)
a Symmetry operation (A): -x þ 1, -y þ 1, -z þ 2.
In both cases, the titration curves (Figures 7b and 8b)
show that the plots for all proton signals exhibit no more
cation-induced shifts above a molar ratio (Ag/L1) of 1.0,
indicating 1:1 (metal-to-ligand) stoichiometries for the res-
pective complexes, which is same as that observed in the
solid state. Above a molar ratio of 1.0, further chemical
Figure 6. Observed isotope distribution of [Ag2(L3)2(NO3)]þ in the
FAB mass spectrum of 4. The bars represent the predicted mass spectral
distribution for this ion.
Figure 7. (a) The 1H NMR spectra of L1 following the stepwise addition of AgClO4 and (b) titration curves for L1 with AgClO4 in CD3CN/CDCl3 (1:1).

Article
Inorganic Chemistry, Vol. 49, No. 16, 2010 7517
Figure 8. (a) The 1H NMR spectra of L2 following the stepwise addition of AgClO4 and (b) titration curves for L2 with AgClO4 in CD3CN/CDCl3 (1:1).
Scheme 3. Copper(I) Complexes Prepared in the Present Study
Figure 9. Crystal structure of5, [Cu2I2(L1)2] CH2Cl2: (a) front view and
(b) side view. The noncoordinating solvent molecule is omitted.
3
shift changes were negligible. Very notably, the magnitude
of the silver(I)-induced chemical shifts (Δδ) for the alipha-
tic protons vary in the sequence: H2 (Δδ: 0.17 ppm) g H3
(0.15 ppm) . H1, H4 (∼0.04 ppm) for L1, and H3 (Δδ: 0.49
ppm) . H4, H2 (0.18 ppm)>H1 (0.13 ppm) for L2. The
observed larger downfield shifts for the protons adjacent
to the S atom relative to those adjacent to oxygen are in
accord with silver(I) being strongly bound to the S donor.
Furthermore, silver(I) causes a relatively much larger shift
Figure 10. Crystal structure of 6, [CuI(L3)] CH2Cl2: (a) front view and
(b) side view. The noncoordinating solvent molecule is omitted.
for the H3 peak (0.49 ppm) in L2 than for the correspond-
3
ing peak in L1 (0.15-0.17 ppm), suggesting that the
binding modes in these complexes could be different
a
;
Preparation and Structure of the Copper(I) Iodide Com-
plexes (5-7). Having obtained four silver(I) complexes,
the coordination products 5-7, showing different topo-
logies, were prepared by the reaction of each ligand with
copper(I) iodide, as depicted in Scheme 3, and in each
case were structurally characterized by X-ray analysis
(Figures 9-11). In this case, the preparation of the cop-
per(I) iodide complex with L2 was not possible.
result that would parallel the different coordination modes
by L1 andL2 toward silver(I), as observed in the solid state.
In addition, the shift for the aromatic proton Ha (0.14
ppm) in L1 is much larger than those for the other aromatic
protons, perhaps reflecting the presence of a related Ag-π
interaction of the type observed in the solid structure of 1.
Consequently, the NMR data suggest that the solution
structures of 1 and 2 are in general agreement with those
occurring in the solid state.
A dichloromethane solution of L1 was allowed to dif-
fuse slowly into an acetonitrile solution of one equivalent

7518 Inorganic Chemistry, Vol. 49, No. 16, 2010
Kang et al.
Figure 11. Crystalstructure of7, {[Cu4I4(L4)2] CH2Cl2}n:(a)basiccoordinationunit, (b) coordinationenvironmentoftheCu4I4-cubanecore, and(c)the
double-stranded 1-D network. The noncoordinating solvent molecule is omitted.
3
˚
˚
Table 6. Selected Bond Lengths (A), Bond Angles (deg), and Torsion Angles
Table 7. Selected Bond Lengths (A), Bond Angles (deg), and Torsion Angles
(deg) for 6
(deg) for 5a
Cu1-S1
2.316(9)
2.660(5)
2.626(4)
2.291(10) Cu2-S4
2.706(5)
2.638(5)
120.07(3)
114.14(3)
100.35(2)
121.76(4)
105.04(3)
110.44(3)
Cu1-S2
Cu1-I1A
Cu1-Cu1A
2.323(8)
2.626(4)
2.802(8)
2.304(10)
2.638(5)
2.701(8)
Cu1-S1
2.303(3)
2.290(3)
93.68(9)
109.15(8)
114.52(8)
59.85(94)
Cu1-S2
2.364(3)
2.554(13)
124.35(10)
93.96(10)
117.04(7)
-59.26(97)
Cu1-I1
Cu1A-I1
Cu1-S3
Cu1-I1
S1-Cu1-S2
S1-Cu1-I1
S2-Cu1-I1
S1-C15-C16-S2
S1-Cu1-S3
S2-Cu1-S3
S3-Cu1-I1
S2-C17-C18-S3
Cu2-S3
Cu2-I2
Cu2-I2A
Cu2A-I2
Cu2-Cu2A
S1-Cu1-I1
S2-Cu1-I1
I1-Cu1-I1A
S3-Cu2-I2
S4-Cu2-I2
I2-Cu2-I2A
S1-Cu1-S2
S1-Cu1-I1A
S2-Cu1-I1A
S3-Cu2-S4
S3-Cu2-I2A
S4-Cu2-I2A
98.12(3)
109.01(2)
115.99(15)
101.45(3)
99.50(3)
distortion appears to reflect the repulsive interaction
between the two sulfur donors in the nine-membered
metallacycle formed upon complexation. It could also
reflect steric crowding in the nine-membered ring because
it has been well established that the bite angle tends to
increase with an increase in chelate ring size. Thus, in this
case, the metallacycle involving Cu-S bonds seems to be
important in the formation of the observed dimeric
structure; in this structure, all three O atoms of L1 remain
uncoordinated. Similar to 1, the large conformational
change in the ligand upon complexation is caused mainly
by altering the torsion angles between two adjacent
donors, changing from the anti [-151.11(63) and
-162.34(41)°] to the gauche form [-65.25(33) and
-46.92(38)°]. Two cases of related dimeric copper(I)
halide complexes of thiamacrocycles with related
structures have been reported by us.2d,3b
Colorless single crystals of complex 6 suitable for X-ray
analysis were obtained directly from the CH3CN/CH2Cl2
reaction mixture containing L3 and CuI. The structure of
6 is shown in Figure 10, with selected geometric para-
meters presented in Table 7. In contrast to 5, the crystallo-
graphic analysis confirms that 6 is a mononuclear com-
plex of formula [CuI(L3)]. The Cu center is facially
coordinated by three S donors from L3, with the fourth
coordination site occupied by an iodide ligand. The two
119.30(16)
S1-C25-C24-O2 -65.25(33)
O2-C23-C22-S2 -46.92(38)
a Symmetry operation (A): -x þ 2, -y, -z þ 1.
of copper(I) iodide in a capillary tube. As apparently no
crystals formed from the diffusion process, crystals of 5
suitable for X-ray analysis were obtained by slow eva-
poration of a CH3CN/CH2Cl2 solution of the comp-
lex. The X-ray structure determination revealed a cofacial
dimeric arrangement of formula [Cu2I2(L1)2] CH2Cl2
3
(Figure 9); two virtually identical independent dimeric
structures are present in the unit cell (Supporting In-
formation). Selected geometric parameters are presented
in Table 6. In this structure, two L1 molecules sandwich
an exodentate diamond-like Cu2I2 core to form a dis-
crete 2:2:2 (metal/ligand/anion) complex incorporating
two Cu-S and two Cu-I bonds to the copper centers.
Each copper(I) is four-coordinate, being bound to two
exo-oriented sulfur atoms from one macrocycle and the
two bridging I atoms. Accordingly, the coordination
sphere of the metal center is very distorted tetrahedral,
with the “tetrahedral” angles ranging from 98.12(3)° for
S1-Cu1-I1 to 120.07(3) for S1-Cu1-S2. In part, the

Article
Inorganic Chemistry, Vol. 49, No. 16, 2010 7519
˚
Table 8. Selected Bond Lengths (A) and Bond Angles (deg) for 7
Cu1-S1
2.307(5)
2.679(2)
2.287(5)
Cu1-I1
2.719(2)
2.646(2)
2.677(2)
Cu1-I2
Cu1-I4
Cu2-S3
Cu2-I2
Cu2-I1
Cu2-I3
2.713(2)
2.691(2)
S1-Cu1-I1
S1-Cu1-I4
S3-Cu2-I2
Cu1-I1-Cu2
I1-Cu1-I2
105.79(13)
110.90(14)
106.76(13)
59.31(7)
S1-Cu1-I2
S3-Cu2-I1
S3-Cu2-I3
Cu1-I2-Cu2
I1-Cu2-I2
102.40(13)
106.35(13)
102.75(13)
59.35(7)
113.86(8)
114.13(8)
Chart 2
Figure 12. Solid-state photoluminescence spectrum of 7 at room tem-
perature (excitation at 350 nm).
That the polymeric structure of 7 contrasts with those
of 5 and 6 is noteworthy in terms of the crystal engineering
approach. Recently, we proposed that simple tuning of
sulfur-to-sulfur separation in dithiamacrocycles repre-
sents a method for controlling the supramolecular struc-
tures of resulting soft metal complexes such as mercury4a,c
and silver.4b,c,10d This approach simply means that if the
separation between two macrocyclic S donors is small in
the macrocyclic cavity, the two S donors will cooperate to
chelate to one metal ion (type A; Chart 2). On the other
hand, if the separation is larger, each S donor will tend to
coordinate to different metal ion centers (type B), leading
to the formation of networked species, although other
factors may also contribute. Applying this concept to the
observed copper(I) iodide complex system in this work,
we realize that the longer sulfur-to-sulfur distance in L4
induces the exobridging coordination (type B) to produce
the polymeric network 7 in contrast to 5 and 6.
macrocyclic O atoms remain uncoordinated. Again, the
coordination sphere of the metal center is distorted tetra-
hedral; the “tetrahedral” angles range from 93.68(9)° for
S1-Cu1-S2 to 124.35(10) for S1-Cu1-S3. The Cu-S
˚
bond lengths [2.657(7)-2.760(3) A] are slightly longer
than reported previously for such bonds.10a,13 Contrast-
ing with this result, we recently reported the preparation
and structure of a dimeric copper(I) iodide complex
which has similar structure to that of 5 but incorporating
a smaller dibenzo-O2S3 macrocycle (17-membered) than
L3 (20-membered).2d,3b Thus, the preference for mono-
nuclear complex formation may be associated with the
greater flexibility of L3, which allows ready metal coordi-
nation to all three consecutive sulfur donors. Thus, the
large conformational change observed in the ligand upon
complexation is also caused by altering the torsion angles
between two adjacent donors, changing from the anti
[-174.83(22) and -174.17(32)°] to the gauche form
[59.85(94) and -59.26(97)°].
Having successfully obtained two different types of
discrete copper(I) iodide complexes of L1 and L3, we
proceeded to the preparation of a corresponding complex
of L4 incorporating a larger cavity and greater sulfur-to-
sulfur distance. Colorless single crystals of 7 (Figure 11
and Table 8) suitable for X-ray analysis were obtained on
slow evaporation of the CH3CN/CH2Cl2 reaction mix-
ture containing L4 and CuI. X-ray analysis revealed that 7
is a rare double-stranded 1-D polymer of type [Cu4I4-
(L4)2]n in which the macrocycles are linked by Cu4I4 cores,
whose geometry resembles a distorted cube with alternat-
ing vertices of Cu and I atoms. Accordingly, the cubane
Cu4I4 units are located at the center of four L4 molecules;
the four copper atoms in each cluster are tetrahedrally
coordinated to three μ3-iodide atoms and one sulfur
donor of L4. In this case, the four Cu-S bonds between
the cubane core and sulfur donors arising from four
different ligands occupy well-separated positions, such
that the adjacent ligand molecules are also arranged
spaciously.
Solid-state photoluminescence studies were carried out
for 5-7 at room temperature. Complexes 5 and 6 were
found to be nonemissive. However, 7 exhibits a bright-green
emission (λem = 553 nm) which is likely due to the presence
of a cluster-centered excited state with mixed halide-to-
metal charge transfer character (see Figure 12).12b,13a,14
Conclusion
We have described the synthesis and structural character-
ization of four sulfur-containing mixed donor macrocycles
and their supramolecular complexes with both silver(I) salts
and copper(I) iodide. The assembly reactions of the macro-
cycles with the respective silver(I) salts employed provide a
facile means of generating different metallo-supramolecules,
including an exocyclic 1-D polymer, an endocyclic mono-
nuclear complex, an endo/exocyclic1-D polymer, and anexo-
cyclic cyclic dimer. From these results, it may be concluded
that the anion-coordination ability and/or the donor varia-
tion have important consequences for the resulting topo-
logies of the silver(I) complexes obtained. Parallel reactions
with copper(I) iodide also afforded less common products,
including an exocyclic dimer, an exocyclic monomer, and a
double-stranded 1-D polymer complex. The versatility of the
(13) (a) Kim, H. J.; Song, M. R.; Lee, S. Y.; Lee, J. Y.; Lee, S. S. Eur. J.
Inorg. Chem. 2008, 3532. (b) Park, K.-M.; Yoon, I.; Seo, J.; Lee, J.-E.; Kim, J.;
Choi, K. S.; Jung, O.-S.; Lee, S. S. Cryst. Growth Des. 2005, 5, 1707. (c) Brooks,
N. R.; Brake, A. J.; Champness, N. R.; Cooke, P. A.; Hubberstey, P.; Proserpio,
(14) (a) Sullivan, R. M.; Martin, J. D. J. Am. Chem. Soc. 1999, 121, 10092.
(b) Henary, M.; Wootton, J. L.; Khan, S. I.; Zink, J. I. Inorg. Chem. 1997, 36, 796.
(c) Liu, P.-H.; Zink, J. I. Inorg. Chem. 1977, 16, 3165.
€
D. M.; Wilson, C.; Schroder, M. J. Chem. Soc., Dalton Trans. 2001, 456.

7520 Inorganic Chemistry, Vol. 49, No. 16, 2010
Kang et al.
ligand systems in generating unusual complex structures has
been discussed with emphasis in particular cases placed on
the influence of the sulfur-to-sulfur distance in control-
ling the topologies of the resulting products. Our present
results clearly show that a small change at the molecular
level (building block or reactant) in the assembly system
can induce a large change at the supramolecular level
(assembled product).
Acknowledgment. This work was supported by WCU
project of MEST and NRF. We would like to express our
thanks to Prof. L. F. Lindoy (The University of Sydney,
Australia) for his helpful advice in preparing manuscript.
Supporting Information Available: Crystallographic data in
CIF format and the additional crystal structures. This material
is available free of charge via the Internet at http://pubs.acs.org.