Materials

All materials were provided by Sigma-Aldrich unless indicated. [2,2':6',2''-terpyridine]-6,6''dicarboxylic acid (H2tda)1, [2,2'-bipyridine]-6,6'-dicarboxylic acid (H2bda)2 and RubdaPic22
(where Pic is Picoline) and RuCl2DMSO43 were synthesized and purified according to the
literature. High-purity deionized water was obtained by passing distilled water through a
nanopure Milli-Q water purification system.
Synthesis of [RuII(tda--N3O)Py2], 1: RuCl2dmso4 (150 mg, 0.31 mmol), 2,2:6,2-terpyridine6,6-dicarboxylic acid (H2tda) (99 mg, 0.31 mmol) and Et3N (0.3 mL) were degassed in dry
MeOH (6 mL), refluxed for 6 hours and cooled down to RT. A brown solid appeared in the
reaction mixture and was filtered, washed with MeOH and Ether. The solid was suspended in
water (5mL) and pyridine (15 mL) and refluxed overnight. The resulting red-wine solution was
cooled to RT and washed with DCM (3x100mL). The watery solution was evaporated and the
red solid was dissolved with MeOH and precipitated with Ether. (95 mg, 0.16 mmol, 51 %
yield). 1H-NMR (500Hz, [d4] Methanol) : 7.09 (4H, t, J=7.5 Hz), 7.58 (2H, tt, J=1.4 and 7.5 Hz),
8.03 (3H, t, J=7.9 Hz), 8.05 (2H, t, J=8.1 Hz), 8.12 (4H, dd, J=1.4 and 7.5 ), 8.15 (2H, d, 7.9 Hz),
8.49 (2H, d, 7.9 Hz), 8.61 (2H, d, J=8.1 Hz). 13C-NMR (500Hz, [d4] Methanol) : 125.2, 125.4,
126.1, 128.1, 133.8, 138.0, 138.1, 153.6, 158.4, 159.6, 163.8, 172.4. UV-vis [max, nm (, M-1 cm1
)]: 236 (21700), 282 (24800), 327 (30700) and 530 (3700). ESI+-HRMS m/z: calc. for RutdaPy2Na+ (C27H19N5NaO4Ru+): 602.03727, found m/z: 602.03678 (0.7 ppm). Anal. Calc. for 13.5 H2O:
C, 50.54%; H, 4.08 %; N, 10.92 %. Found: C, 50.46 %; H, 3.78 %; N, 10.87%.
Synthesis of [RuIII(tda--N3O)Py2] [PF6], (2)(PF6): A solution of Ceric Ammonium Nitrate (CAN)
(1.82 mM, 1.05 eq, 2mL) was added drop wise to a solution of 1 in triflic acid (1.72 mM, 25 mL)
and the mixture was stirred for 15 minutes. A green powder was obtained when a saturated
solution of KPF6 was added. The suspension was centrifuged for 10 minutes, the solid filtrated
and washed with water, methanol and ether (12 mg, 39%). UV-vis [max, nm (, M-1 cm-1)]: 279
(25800, 322 (13200) and 441 (1300). Anal. Calc. for (2)(PF6)0.5 H2O : C, 44.27%; H, 2.75 %; N,
9.56 %. Found: C, 44.23 %; H, 2.50 %; N, 9.39%.
Synthesis of [RuIV(tda--N3O2)Py2] [PF6], (3)(PF6)2. A solution of CAN (3.64 mM, 2.1 eq, 2mL) was
added drop wise to a solution of 1 in triflic acid (1.72 mM, 25 mL) and the mixture was stirred
for 15 minutes. A brown powder was obtained when a saturated solution of KPF6 was added.
The suspension was centrifuged for 10 minutes, the solid filtrated and washed with cold water
and ether (12 mg, 32%). 1H-NMR (500 Hz, D2O) : 7.24 (4H, t, J=7.0 Hz), 7.70 (6H, m), 8.20 (2H,
d, J=7.8 Hz), 8.62 (2H, t, J=7.8 Hz), 8.93 (2H, d, J=7.8 Hz), 8.98 (1H, d, J=7.9 Hz), 9.08 (2H, d,
J=7.9 Hz). 13C-NMR (500Hz, D2O) : 127.3, 123.0, 131.0, 132.2, 141.5, 147.3, 147.6, 150.3,
152.5, 157.8, 157.9, 168.0. UV-vis [max, nm (, M-1 cm-1)]: 280 (23600) and 347 (6800).

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