Paper
RSC Advances
ꢁ
1
ꢁ1
(
SCH
2
), 32.0 (SCH
2
), 30.9 (SCH
2
). IR (cm ): 3361 (OH), 689 43.1 (OCH
2
), 39.4 (SCH
2
), 34.4 (SCH
2
), 32.4 (CH
3
). IR (cm ):
(
CH –S–CH ).
1348, 1152 (CH –SO ), 679 (CH –S–CH ).
2
2
3
2
2
2
3,6-Dithiaoctane-1,8-dimesylate. This compound was
1,13-Dioxa-4,7,10-trithiacyclopentadecano[2,3-f][1,10]-phenan-
prepared following a procedure similar to the synthesis of 2- throline (L3). This compound was prepared following a procedure
(
(
methylthio)ethylmesylate
using
3,6-dithiaoctane-1,8-diol similar to the synthesis of 1,10-dioxa-4,7-dithiacyclobutaoctano
3.64 g, 20 mmol), pyridine (8.0 ml, 0.1 mol) and meth- [2,3-f][1,10]-phenanthroline using 1,10-phenanthroline-5,6-diol
anesulfonyl chloride (4.6 ml, 60 mmol). The mixture was stirred (0.22 g, 1 mmol), 3,6,9-trithiaundecane-1,11-dimesylate (0.4 g, 1
for 3 h. Subsequent purication gave a pale yellow oil which mmol) and Cs CO (0.98 g, 3 mmol) in dry DMF (40 ml). Yield:
formed a white solid on standing. Yield: 4.72 g (70%). H NMR 0.24 g (57%). H NMR (400 MHz, CDCl
): d ¼ 9.17 (dd, 2H, phen,
400 MHz, CDCl ): d ¼ 3.66 (m, 4H, OCH ), 2.96–2.89 (m, 8H, J ¼ 4.5 Hz, J ¼ 1.7 Hz), 8.67 (m, 2H, phen), 7.69 (m, 2H, phen),
2
3
1
1
3
(
3
2
1
2
1
3
SCH ), 2.81 (s, 6H, CH ); C NMR: 43.1 (OCH ), 39.6 (SCH ), 4.46 (dt, 4H, OCH , J ¼ 7.0 Hz, J ¼ 7.0 Hz), 3.08 (m, 4H, SCH ),
2
3
2
2
2
1
2
2
ꢁ
1
13
3
4.4 (SCH ), 32.6 (CH ). IR (cm ): 1352, 1173 (CH –SO ), 677 2.95–2.78 (m, 8H, SCH ); C NMR: 149.7, 141.7, 131.2, 130.5,
2
3
3
2
2
ꢁ1
(CH
2
–S–CH
2
).
125.6, 123.3 (phen); 73.7 (OCH ), 32.9, 31.7 (SCH
2
2
). IR (cm ):
1
,10-Dioxa-4,7-dithiacyclobutaoctano[2,3-f][1,10]-phenanthro- 1695 (C]N), 674 (CH
line (L2). A mixture of 1,10-phenanthroline-5,6-diol (0.17 g, 0.8 419.0877 (419.0920) ([M + H] ).
mmol), 3,6-dithiaoctane-1,8-dimesylate (0.26 g, 0.8 mmol) and 3,6,9,12-Tetrathiatetradecane-1,14-diol. 3,6-dithiaoctane-1,8-
Cs CO (0.75 g, 2.4 mmol) in dry DMF (40 ml) was added into dithiol was prepared by converting 3,6-dithiaoctane-1,8-diol to
2
–S–CH ). ESI-MS: m/z calcd (found)
2
+
2
3
17
a pre-dried Schlenk tube under an atmosphere of dry nitrogen. the dithiol according to the literature procedure. 3,6,9,12-
The tube was then sealed and the mixture stirred at 85 C for Tetrathiatetradecane-1,14-diol was prepared by reacting 3,6-
ꢂ
48 h. Aer the reaction was complete, the system was le to cool dithiaoctane-1,8-dithiol (2.0 g, 9 mmol) and 2-chloroethanol
down to room temperature and ltered to remove inorganic salts. (1.4 ml, 21 mmol) in the same manner as 3,6-dithiaoctane-1,8-diol.
1
The ltrate was evaporated, the product obtained dissolved in Yield: 2.1 g (74%). H NMR (400 MHz, CDCl
CH Cl , J ¼ 5.9 Hz), 3.12–2.76 (m, 16H, OCH ), 2.30 (br s, 2H, OH);
(50 ml) and washed with brine (2 ꢀ 50 ml). The organic OCH
layer was collected, dried over MgSO C NMR: 60.7 (CH OH), 41.8 (SCH ), 35.4 (SCH
reduced pressure to give a brown oil. Purication of the product 31.9 (SCH ), 29.7 (SCH ). IR (cm ): 3291 (OH), 678 (CH
by ash column chromatography on alumina with chlor- 3,6,9,12-Tetrathiatetradecane-1,14-dimesylate.
oform : hexane (1 : 1, v/v) yielded a white solid. Yield: 0.14 g compound was prepared following a procedure similar to the
3
): d ¼ 3.78 (t, 4H,
2
2
2
2
13
4
and evaporated under
2
2
2
), 32.4 (SCH
2
),
).
ꢁ
1
2
2
2
–S–CH
2
This
1
(
50%). H NMR (400 MHz, CDCl ): d ¼ 9.17 (dd, 2H, phen, J ¼ synthesis of 3,6-dithiaoctane-1,8-dimesylate using 3,6,9,12-
3
1
4
7
4
3
.3 Hz, J
.68 (dd, 2H, phen, J
2
¼ 1.6 Hz), 8.50 (dd, 2H, phen, J
1
¼ 8.3 Hz, J
2
¼ 1.6 Hz), tetrathiatetradecane-1,14-diol (1.6 g, 5.3 mmol), pyridine
1
¼ 8.3 Hz, J
2
¼ 4.3 Hz), 4.59 (m, 2H, OCH
2
), (1.3 ml, 16 mmol) and methanesulfonyl chloride (1.3 ml, 16
1
.46 (dt, 2H, OCH
.09 (d, 2H, SCH
, J ¼ 6.3 Hz), 2.96 (dd, 2H, SCH
7.7 Hz), 2.82 (m, 2H, SCH
30.5, 128.7, 122.7 (phen); 76.1 (OCH ), 31.7, 29.7 (SCH ). IR (cm ): 1345, 1171 (CH –SO ), 679 (CH –S–CH ).
2
, J
1
¼ 12.5 Hz, J
2
¼ 6.2 Hz), 3.18 (m, 2H, SCH
, J
); C NMR: 149.6, 142.5, 132.8, NMR: 43.1 (OCH
2
), mmol). Yield: 1.9 g, (78%). H NMR (400 MHz, CDCl
(m, 4H, OCH ), 2.94 (s, 6H, CH ), 2.84–2.72 (m, 16H, SCH
), 39.1 (SCH ), 34.5 (SCH ), 32.5 (CH
3
): d ¼ 3.60
1
3
2
2
1
¼ 10.7 Hz, J
2
2
3
2
);
C
1
3
¼
2
2
2
2
3
). IR
ꢁ1
1
2
2
3
2
2
2
ꢁ
1
(
3
cm ): 1671 (C]N), sh (CH –S–CH ). ESI-MS: m/z calcd (found)
1,15-Dioxa-4,7,10,13-tetrathiacyclohexadodecano[2,3-f][1,10]-
phenanthroline (L4). A mixture of NaH (0.10 g of 60% mineral
2
+
2
59.0843 (359.0887) ([M + H] ).
3
,6,9-Trithiaundecane-1,11-diol. This compound was oil dispersion, 2.5 mmol) and 1,10-phenanthroline-5,6-diol
prepared following a procedure similar to the synthesis of 3,6- (0.25 g, 1.2 mmol) in dry DMF (20 ml) was discharged into
dithiaoctane-1,8-diol using 3-thiapentane-1,5-dithiol (8.0 ml, 60 a ask under N and the mixture stirred for 10 min. A solution of
2
mmol) in place of ethane-1,2-dithiol. Aer reuxing for 4 h, the 3,6,9,12-tetrathiatetradecane-1,14-dimesylate (0.55 g, 1.2 mmol)
reaction mixture was cooled to room temperature, the organic in degassed DMF (20 ml) was then added and the mixture
ꢂ
layer decanted while the white residue was treated with hot reuxed at 80 C for 24 h. Aer completion of the reaction, the
acetone (100 ml) and then ltered. The organic phases were reaction mixture was ltered, concentrated and water (30 ml)
combined, evaporated to dryness and the resulting solid tritu- added. The target compound was extracted with several small
rated with diethyl ether to yield a white solid. Yield: 11.24 g portions of CH
2
Cl
and evaporated under vacuum to give a brown oil.
), 2.30 (br s, 2H, OH); C NMR: Purication by chromatography on silica using 10% methanol in
2
, the organic phases combined, dried over
1
(
76%). H NMR (400 MHz, CDCl
3
): d ¼ 3.85 (d, 4H, OCH
2
, J ¼ 5.1 MgSO
4
1
3
Hz), 2.90–2.81 (m, 12H, SCH
6
3
2
ꢁ
1
1
0.7 (CH
292 (OH), 680 (CH
,6,9-Trithiaundecane-1,11-dimesylate. This compound was 1.8 Hz), 8.61 (dd, 2H, phen, J ¼ 7.9 Hz, J ¼ 1.8 Hz), 7.66 (dd,
2
OH), 35.4 (SCH
2
), 32.4 (SCH
2
), 32.0 (SCH
2
). IR (cm ): dichloromethane yielded a white solid. Yield: 0.24 g (43%). H
2
–S–CH
2
).
NMR (400 MHz, CDCl ¼ 4.7 Hz, J
3
): d ¼ 9.16 (dd, 2H, phen, J
1
2
¼
3
1
2
prepared following a procedure similar to the preparation of 2H, phen, J ¼ 7.9 Hz, J ¼ 4.7 Hz), 4.46 (dd, 4H, OCH , J ¼
1
2
2
1
1
3
3
,6-dithiaoctane-1,8-dimesylate using
a
mixture of 3,6,9- 8.0 Hz, J ¼ 3.0 Hz), 3.08–2.77 (m, 16H, SCH ); C NMR: 149.6,
2
2
trithiaundecane-1,11-diol (2.42 g, 10 mmol), pyridine (4.0 ml, 50 142.1, 137.2, 131.2, 125.8, 122.9 (phen); 72.9 (OCH
2
), 32.4, 31.6,
–S–CH ). ESI-MS:
ꢁ
1
mmol) and methanesulfonyl chloride (2.3 ml, 30 mmol). Yield: 29.7 (SCH
2
). IR (cm ): 1684 (C]N), 688 (CH
2
2
1
+
2.45 g (62%). H NMR (400 MHz, CDCl
3
): d ¼ 3.67 (m, 4H, m/z calcd (found) 479.0911 (479.0954) ([M + H] ).
13
OCH ), 2.95–2.82 (m, 12H, SCH ), 2.80 (s, 6H, CH
2
2
3
); C NMR:
[Ru(bpy)
2
(L1)][PF
6 2
] (1). A mixture of L1 (55 mg, 0.17 mmol)
and [Ru(bpy)
2
2
Cl ]$2H
2
O (90 mg, 0.17 mmol) in ethanol (50 ml)
This journal is © The Royal Society of Chemistry 2018
RSC Adv., 2018, 8, 3663–3672 | 3665