Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany

2 Tris(2,2 -bipyridyl)ruthenium with Branched Polyphenylene Shells: A New Family of Charged Shape Persistent Nanoparticles Monika C. Haberecht, Jan M. Schnorr, Ekaterina V. Andreitchenko, Christopher G. Clark, Jr., Manfred Wagner, and Klaus Müllen* Experimental: Instrumentation: 1 H and 13 C NMR spectra were recorded on Bruker DPX250, DRX300, DRX500, and DRX700 spectrometers, respectively, and referenced to residual signals of the deuterated solvent. Abbreviations: s = singlet, d = doublet, t = triplet, n.r. = multiplet expected but not resolved; the numbering of the 2,2 -bipyridyl resonances is in agreement with the IUPAC specifications. Field desorption mass spectra (FDMS) were performed with a VG- Instruments ZAB 2-SE-FDP using 8 kv accelerating voltage. MALDI-TOF mass spectra were measured using a Bruker Reflex II, calibrated against poly(ethylene glycol) (3.000 g/mol). Samples for MALDI-TOF MS were prepared by mixing the analyte with the matrix (dithranol or 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB) [1] ) in dichloromethane in a ratio of 1/250. Due to the sensitivity of the ruthenium complexes, fragmentation products missing one or even two 2,2 -bipyridyl ligands were generated during most measurements due to an overlap in the laser emission with the dendrimer absorption. Molecular models of dendrimers were generated using POV-Ray and are qualitatively similar to the results of MMFF94 molecular mechanics calculations. Elemental analyses were performed by the Microanalytical Laboratory of Johannes Gutenberg University and were carried out for all 2,2 -bipyridyls up to the second generation. The nature of the polyphenylene molecules to function as hosts for small quantities of solvent impurities as well as incomplete combustion limits the effectiveness of elemental analyses, and the results varied significantly from the expected results. As such, MALDI-TOF in combination with 1 H NMR were relied upon more heavily than the elemental analyses data. Some MALDI-induced fragmentation of the dendrimers at the weakest bonds [6] was typically observed (Figure S2, S3). Increasing the laser power induced further fragmentation, and 1 H NMR showed no indication of fragmentation products (The bipyridyl resonances are particularly sensitive to the coordination environment). 1

3 Materials: 2-bromo-4-iodopyridine 3, [2] Ru(DMSO) 4 Cl [3] 2, and cyclopentadienones 10 [4] and 11 [5] were synthesized according to literature procedures. All other chemicals and solvents were purchased from Aldrich or Acros and used without further purification. Reactions were all carried out under Argon atmosphere. Syntheses: 4,4 -Bis(ethynyl)-2,2 -bipyridyl (1). A solution of TBAF x 3H 2 O (0.290 g, mmol) in dry THF (2 ml) was added dropwise to a solution of 2 (0.238 g, mmol) in dry THF (3 ml). The reaction mixture was stirred at ambient temperature for 30 min before water (2 ml) was added. The product was extracted into dichloromethane (3 x 20 ml), the organic layers were combined, washed with brine and dried over Na 2 SO 4. Evaporation of the solvent gave an oily residue from which 1 was observed as a colorless powder upon reprecipitation in n-pentane. Yield: g, 89%. 1 H NMR (250 MHz, CDCl 3, 300 K): =8.66 (d, 2H, 3 J(H,H)=5.0 Hz; H6), 8.48 (n.r., 2H; H3), 7.38 (dd, 2H, 3 J(H,H)=5.0 Hz, 4 J(H,H)=1.5 Hz; H5), 3.32 (s, 2H; C C-H) ppm; 13 C NMR (75 MHz, CDCl 3, 300 K): =155.58, , , , , 81.87, ppm; FDMS (80 ev): m/z (%) = (100) [M + ]; elemental analysis calcd (%) for C 14 H 8 N 2 (204.23): C 82.33, H 3.95, N 13.72; found: C 81.15, H 4.06, N ,4 -Bis(triisopropylsilylethynyl)-2,2 -bipyridyl (2): 4 (1.582 g, mmol) was dissolved in dry toluene (50 ml) and Sn 2 (n-bu) 6 (1.356 g, mmol) was added from a syringe. Argon was bubbled through the solution for 1 h before Pd(PPh 3 ) 4 (0.135 g, mmol) was added and the mixture was stirred at 120 C for 7 d. After cooling to RT, the reaction mixture was poured into aqueous EDTA and the product was extracted into chloroform (3 x 50 ml). The organic layers were combined, washed with brine und dried over Na 2 SO 4. Evaporation of the solvent gave a dark residue which was chromatographed on silica (eluent: dichloromethane) to give 2 as colourless crystals. Yield: g, 65%. 1 H NMR (250 MHz, CD 2 Cl 2, 300 K): =8.61 (d, 2H, 3 J(H,H)=5.0 Hz, H6), 8.44 (s, 2H, H3), 7.36 (dd, 2H, 3 J(H,H)=5.0 Hz, 4 J(H,H)=1.5 Hz, H5), 1.16 (s, 42H, TiPS) ppm; 13 C NMR (75 MHz, CD 2 Cl 2, 300 K): =156.0, 149.5, 132.7, 126.4, 123.5, 104.7, 96.9, 18.8, 11.6 ppm; FDMS (80 ev): m/z (%) = (100) [M + ]; elemental analysis calcd (%) for C 32 H 48 N 2 Si 2 (516,91): C 74.35, H 9.36, N 5.42; found: C 73.75, H 9.42, N

4 2-Bromo-4-(triisopropylsilylethynyl)pyridine (4). 3 (0.737 g, mmol), Pd(PPh 3 ) 2 Cl 2 (0.914 g, mmol) and CuI (0.050 g, mmol) were dissolved in a mixture of toluene (10 ml) and triethylamine (20 ml). The resulting solution was degassed and cooled to 0 C before triisopropylsilylacetylene (0.427 g, 2.35 mmol) was added from a syringe thereby maintaining the temperature. After the addition was completed, the reaction mixture was allowed to warm to RT overnight and dichloromethane and water were added. The phases were separated, the organic layer was washed with sat. NH 4 Cl (aq), cold HCl (1 N), 10% NaHCO 3 (aq), dried over MgSO 4, and concentrated in vacuo. The crude material was purified by means of column chromatography on silica using dichloromethane/petroleum ether (1/1) as an eluent. Upon evaporation of the solvent, 4 was obtained as a colorless liquid. Yield: g, 67%. 1 H NMR (250 MHz, CD 2 Cl 2, 300 K): =8.29 (d, 2H, 3 J(H,H)=5.0 Hz; H6), 7.53 (s, 2H; H3), 7.28 (dd, 2H, 4 J(H,H)=1.2 Hz, 3 J(H,H)=5.0 Hz; H5), 1.13 (s, 42H, TiPS) ppm; 13 C NMR (75 MHz, CD 2 Cl 2, 300 K): =150.29, , , , , , 99.15, 18.71, ppm; FDMS (80 ev): m/z (%) = (100) [M + ]. 4,4 -Bis(1,2,3,4-tetraphenylphenyl)-2,2 -bipyridyl (5). 1 (0.056 g, mmol) and 2,3,4,5-tetraphenylcyclopentadienone (0.262 g, mmol,) were put under Argon, dissolved in o-xylene (2 ml) and stirred at 141 C for 24 h. After cooling to RT, the reaction mixture was evaporated to dryness. The residue was chromatographed on silica using first dichloromethane and then dichloromethane/methanol (50/1) as eluents. Upon evaporation of the solvent, 5 was obtained as a white powder. Yield: g, 97%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): =8.37 (n.r., 2H; H3-bpy), 8.28 (d, 2H, 3 J(H,H)=5.0 Hz; H6-bpy), 7.58 (s, 2H), 7.17 (n.r., 10H), (n.r., 30H), (n.r., 2H) ppm; 13 C NMR (125 MHz, CDCl 3, 302 K): = (bpy-c2), (bpy-c4), (bpy-c6), , , , , , , , , , , , , , , , , , , , , , ppm; FDMS (80 ev): m/z (%) = (100) [M + ], (53) [ M] 2+ ; elemental analysis calcd (%) for C 70 H 48 N 2 (917.14): C 91.67, H 5.28, N 3.05; found: C 90.52, H 5.66, N ,4 -Bis[G2]-2,2 -bipyridyl (6). A solution of 1 (0.014 g, mmol) and 10 (0.235 g, mmol) in o-xylene (2 ml) was stirred at 140 C for 2 d. The reaction mixture was absorbed on silica and eluted employing 3

5 first dichloromethane and then ethyl acetate. The obtained product was further purified by reprecipation in n-pentane to give 6 as a pale yellow solid. Yield: g, 90%. 1 H NMR (500 MHz, CD 2 Cl 2, 302 K): =8.32 (n.r., 2H; H3-bpy), 8.25 (d, 2H, 3 J(H,H)=5.0 Hz; H6- bpy), 7.55 (s, 2H), 7.44 (s, 2H), 7.34 (s, 2H), (n.r., 26H), (n.r., 4H), (n.r., 50H), (n.r., 18H), (n.r., 8H), 6.70 (d, 4H, 3 J(H,H)=8.5 Hz), 6.59 (d, 4H, 3 J(H,H)=8.5 Hz), 6.53 (d, 4H, 3 J(H,H)=8.4 Hz) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 302 K): = (2C, bpy-c2), (2C, bpy-c4), (2C, bpy- C6), (4C), (4C), (2C), (2C), (2C), (4C), (4C), (2C), (2C), (4C), (4C), (2C), (2C), (2C), (2C), (4C), (2C), (2C), (2C), (2C), (2C), (2C), (26C), (6C), (8C), (12C), (4C), (4C), (4C), (8C), (4C), (16C), (8C) (2C), (4C), (2C), (8C), (4C), (2C), (2C) ppm; FDMS (80 ev): m/z (%) = (100) [M + ], (19) [ M] 2+ ; elemental analysis calcd (%) for C 190 H 128 N 2 ( ): C 93.56, H 5.29, N 1.15; found: C 93.11, H 5.58, N ,4 -Bis[G3]-2,2 -bipyridyl (7). A mixture of 13 (0.080 g, mmol) and 10 (0.407 g, mmol) was dissolved in o- dichlorobenzene (5 ml) and stirred at 175 C for 3 d. After cooling down to RT the reaction mixture was precipitated into petroleum ether and the crude product was collected on a frit. Column chromatography on silica with dichloromethane and then dichloromethane/net 3 (50/1) as eluents followed by reprecipitation in n-pentane gave 7 as pale yellowish solid. Yield: g, 41%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =8.31 (s, 2H; H3-bpy), 8.25 (d, 2H, 3 J(H,H) = 5.1 Hz; bpy-h6), 7.53 (s, 2H), 7.43 (s, 2H), 7.42 (s, 2H), 7.39 (s, 2H), 7.38 (2s, 4H), 7.33 (s, 2H), (n.r., 250H), 6.56 (n.r., 10H), (n.r., 10H) ppm; 13 C NMR (175 MHz, CD 2 Cl 2, 303 K): =156.22, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ppm; MALDI-TOF (dithranol): m/z (%): 5484 (100) [M + ]. 4,4 -Bis[G4]-2,2 -bipyridyl (8). 4

6 A solution of 15 (0.020 g, mmol) and 10 (0.087 g, mmol) in o-dichlorobenzene (2 ml) was heated at 175 C for 3d. The reaction mixture was precipitated in n-pentane and the product was collected on a frit. Further purification by column chromatography on silica with first dichloromethane and then dichloromethane/methanol (40/1) followed by reprecipitation in MeOH to gave 8 as a yellowish solid. Yield: g, 39%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): =8.31 (s, 2H; bpy-h3), 8.22 (d, 2H, 3 J(H,H) = 5.2 Hz; bpy-h6), 7.51(s, 2H), 7.40 (5s, 10H), 7.36 (4s, 8H), 7.35 (3s, 6H), 7.30 (2s, 4H), (n.r., 574H) ppm; 13 C NMR (75 MHz, CDCl 3, 303 K): =155.96, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ppm; MALDI-TOF (dithranol): m/z (%): (100) [M + ]. 4,4 -Bis(1,4-diphenyl-2,3-((p-TiPS-ethynyl)phenyl)phenyl)-2,2 -bipyridyl (12). In an Argon atmosphere, a solution of 1 (0.020 g, mmol) and 11 (0.183 g, mmol) in o-xylene (2 ml) was stirred at 140 C for 18 h until the FD mass spectrum indicated the completeness of the reaction. The reaction mixture was cooled to RT, absorbed on silica and the product was purified via column chromatography with first dichloromethane/petroleum ether (3/1) and then dichloromethane/net 3 (50/1). After repricipitation in n-pentane, 12 was obtained as a colourless solid. Yield: g, 48%. 1 H NMR (300 MHz, CDCl 3, 300 K): =8.34 (n.r., 2H; bpy-h3), 8.27 (d, 2H, 3 J(H,H)=5.0 Hz; bpy-h6), 7.57 (s, 2H), (n.r., 10H), 7.09 (d, 4H, 3 J(H,H)=8.3 Hz), (n.r., 10H), (n.r., 10H), 6.80 (d, 4H, 3 J(H,H)=8.3 Hz), 1.09 (s, 42H, TiPS), 1.08 (s, 42H, TiPS) ppm; 13 C NMR (75 MHz, CD 2 Cl 2, 300 K): = (bpy-c2), (bpy-c4), (bpy-c6), , , , , , , , , , , , , , , , , , , , , , , , , 91.09, 90.93, 18.77, ppm; FDMS (80 ev): m/z (%) = (100) [M + ]. 4,4 -Bis(1,4-diphenyl-2,3-(p-ethynylphenyl)phenyl)-2,2 -bipyridyl (13). TBAF (0.154 g, mmol) was dissolved in THF (2 ml) and added dropwise to a solution of 12 (0.200 g, mmol) in THF (3 ml) at ambient temperarute. The reaction mixture was stirred for 1 h and then quenched by addition of water. After the THF was removed in vacuo, the residue was extracted with dichloromethane/water, and the organic layer was repeatedly washed with brine. After drying over Na 2 SO 4 and evaporation of the solvent, the crude 5

7 product was further purified by precipitation in n-pentane to give 13 as a colourless solid. Yield: g, 98%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): =8.37 (n.r., 2H; bpy-h3), 8.28 (d, 2H, 3 J(H,H)=5.0 Hz; bpy-h6), 7.60 (s, 2H), (n.r., 6H), (n.r., 4H), 7.10 (d, 4H, 3 J(H,H)=8.3 Hz), 7.04 (d, 4H, 3 J(H,H)=8.3 Hz), (n.r., 6H), (n.r., 4H), 6.89 (dd, 2H, 3 J(H,H)=5.1 Hz, 4 J(H,H)=1.7 Hz; H5-bpy), 6.85 (d, 4H, 3 J(H,H)=8.3 Hz), 6.79 (d, 4H, 3 J(H,H)=8.3 Hz), 3.05 (s, 2H; C C-H), 3.02 (s, 2H; C C-H) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 303 K): = (C2-bpy), (C4-bpy), (C6-bpy), , , , , , , , , , , , , , , , , , , , , , , , 83.73, 77.49, ppm; FDMS (80 ev): m/z (%) = (100) [M + ], (35) [ M] 2+ ; elemental analysis calcd (%) for C 78 H 48 N 2 ( ): C 92.46, H 4.77, N 2.76; found: C 89.93, H 5.43, N ,4 -Bis([G2](TiPS-ethynyl) 4 )-2,2 -bipyridyl (14). A mixture of 13 (0.049 g, mmol,) and 11 (0.193 g, mmol,) was dissolved in o- xylene (3 ml) and stirred at 141 C for 2 d. After cooling to RT the reaction mixture was absorbed on silica and chromatographed using first dichloromethane and then dichloromethane/methanol (20/1) as eluents. Reprecipitation in methanol yielded 14 as a colourless solid. Yield: g, 90%. 1 H NMR (250 MHz, CD 2 Cl 2, 300 K): =8.32 (n.r., 2H; H3-bpy), 8.24 (d, 2H, 3 J(H,H)=5.2 Hz; H6-bpy), 7.54 (s, 2H), 7.42 (s, 2H), 7.38 (s, 2H), (n.r., 18H), (n.r., 8H), (n.r., 12H), (n.r., 8H), (n.r., 18H), (n.r., 14H), 6.77 (m, 10H), 6.73 (m, 10H), 6.66 (d, 4H, 3 J(H,H)=8.3 Hz), 6.57 (d, 4H, 3 J(H,H)=8.3 Hz), 6.51 (d, 4H, 3 J(H,H)=8.3 Hz), 1.10 (s, 168 H, TiPS) ppm; 13 C NMR (175 MHz, CD 2 Cl 2, 303 K): = (C2-bpy), (C4-bpy), (C6-bpy), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 90.95, 90.85, 18.79, ppm; elemental analysis calcd (%) for C 278 H 288 N 2 Si 8 ( ): C 86.01, H 7.48, N 0.72; found: C 84.83, H 7.73, N MALDI-TOF (dithranol): m/z (%): 3883 (100) [M + ]. 4,4 -Bis([G2](ethynyl) 4 )-2,2 -bipyridyl (15). TBAF (0.065 g mmol) was dissolved in THF (1.5 ml) and added dropwise to a solution of 14 (0.100 g, mmol) in THF (1.5 ml) at RT. The reaction mixture was stirred 6

8 at ambient temperature for 1 h before water was added and the THF was removed in vacuo. The product was extracted from the remaining residue into dichloromethane, repeatedly washed with brine and dried over Na 2 SO 4. After evaporation of the solvent, the residue was dissolved in dichloromethane (2 ml) and precipitated into n-pentane to give 15 as a colourless solid that was collected on a frit and dried in vacuo. Yield: g, 48%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): =8.30 (n.r., 2H; bpy-h3), 8.23 (d, 2H, 3 J(H,H)=5.1 Hz; bpy- H6), 7.53 (s, 2H), 7.43 (s, 2H), 7.39 (s, 2H), 7.18 (n.r., 18H), (n.r., 8H), (n.r., 12H), (n.r., 8H), (n.r., 18H), (n.r., 14H); (n.r., 20H), 6.66 (d, 4H, 3 J(H,H)=8.3 Hz), 6.57 (d, 4H, 3 J(H,H)=8.3 Hz), 6.51 (d, 4H, 3 J(H,H)=8.3 Hz), 3.03 (2s, 4H, C C-H), 3.02 (s, 2H, C C-H), 3.01 (s, 2H, C C-H) ppm; 13 C NMR (75 MHz, CD 2 Cl 2, 300 K): =156.11, , , , , , , , , , , , , , , , , (2x), , , , , , , , , , , , , , , , , , , , , , , , , , , , , 83.78, 77.40, ppm; MALDI- TOF (dithranol): m/z (%): 2632 (100) [M + ]; elemental analysis calcd (%) for C 206 H 128 N 2 ( ): C 94.03, H 4.90, N 1.06; found: C 92.20, H 5.08, N [Ru(4,4 -bis(1,2,3,4-tetraphenylphenyl)-2,2 -bipyridyl) 3 ]Cl 2 (16). 5 (0.150 g, mmol) and Ru(DMSO) 4 Cl 2 (0.025 g, mmol) were dissolved in DMF (2.5 ml) and stirred at 140 C for 3 d. The reaction mixture was evaporated to dryness, the remaining dark residue was absorbed on silica and chromatographed using dichloromethane/methanol (20/1) as an eluent. Upon evaporation of the solvent 16 was obtained as in intense red powder. Yield: g, 55%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =7.74 (d, 6H, 4 J(H,H)=1.7 Hz; bpy-h3), 7.60 (s, 6H), 7.27 (d, 6H, 3 J(H,H)=5.9 Hz; bpy- H6), 7.19 (s, 30H), 7.16 (dd, 6H, 3 J(H,H)=5.9 Hz, 4 J(H,H)=1.7 Hz; bpy-h5), (n.r., 18H), (n.r., 72H) ppm; 13 C NMR (75 MHz, CD 2 Cl 2, 300 K): =156.16, , , , , , , , , , , , , , , , , , , , , , , , , ; MALDI-TOF (DCTB): m/z (%): 2915 [M + ], 2878 [M-1Cl] +, 2853 [M-2Cl] +, 1972 [M-1bpy-1Cl] +. [Ru(4,4 -bis[g2]-2,2 -bipyridyl) 3 ]Cl 2 (17). A mixture of 6 (0.070 g, mmol) and Ru(DMSO) 4 Cl 2 (0.004 g, mmol) in DMF (1 ml) was stirred at 140 C for 3 d. After 7

9 cooling to RT the reaction mixture was poured into water and extracted with dichloromethane (3 x). The combined organic layers were washed with brine and dried over MgSO 4. A dark solid remained that was chromatographed on silica using dichloromethane/methanol (20/1) as an eluent to give 17 as an intense red solid. Yield: g, 23%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): =7.58 (n.r., 6H; bpy-h3), 7.53 (s, 6H), 7.42 (s, 6H), 7.37 (s, 6H), 7.25 (d, 6H, 3 J(H,H)=5.9 Hz; bpy-h6), (n.r., 18H), 7.16 (n.r., 36H), 7.15 (n.r., 24H), (n.r., 12H), 7.08 (n.r., 6H; bpy-h5), (n.r., 36H), (n.r., 186H), (n.r., 12H), 6.55 (d, 12H, 3 J(H,H)=8.5 Hz), 6.48 (d, 12H, 3 J(H,H)=7.7 Hz) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 303 K): =156.08, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ppm; MALDI-TOF (DCTB): m/z (%):7419 (100) [M-2Cl] +, 5051 [M- 1bpy] +, 5017 [M-1bpy-1Cl] +. [Ru(4,4 -bis[g3]-2,2 -bipyridyl) 3 ]Cl 2 (18). Ru(DMSO) 4 Cl 2 (0.002 g, mmol) and 7 (0.075 g, mmol) were dissolved in DMF (1.5 ml) and stirred at 140 C for 3d. After cooling to RT, water was added and the product was extracted into dichloromethane. 18 was obtained as a dark red microcrystalline solid after column chromatography on silica (eluent: dichloromethane/methanol 20 /1) and recrystallized upon evaporation of its methanolic solution. Yield: g, 44%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): =7.58 (n.r., 6H; bpy-h3), 7.49 (s, 6H), 7.40 (2s, 12H), 7.36 (3s, 18H), 7.23 (s, 12H), (n.r., 798H), (n.r., 6H), 6.44 (n.r., 6H) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 303 K): =156.09, , n.r., , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ppm; MALDI-TOF (DCTB): m/z = [M-1Cl] +. [Ru(4,4 -bis(1,4-diphenyl-2,3-((p-tipsethynyl)phenyl)phenyl)-2,2 -bipyridyl) 3 ]Cl 2 (19). A mixture of 12 (0.300 g, mmol) and Ru(DMSO) 4 Cl 2 (0.028 g, mmol) in DMF (5 ml) was stirred at 140 C for 4 d. After cooling to RT the mixture was poured into water and extracted with dichloromethane (3x). The organic layers were combined, washed with brine and the solvent was evaporated. After purification by column chromatography on silica using 8

10 dichloromethane/meoh (20/1) as an eluent, 19 was isolated as an intense red solid. Yield: g, 48%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =7.70 (n.r., 6H; bpy-h3), 7.61 (s, 6H), 7.28 (n.r., 6H) 7.23 (n.r., 18H), 7.18 (n.r., 12H), 7.15 (n.r., 6H), 7.10 (d, 12H, 3 J(H,H)=8.0 Hz), 7.05 (d, 12H, 3 J(H,H)=7.2 Hz), (n.r., 42H), 6.78 (d, 12H, 3 J(H,H)=7.2 Hz), 1.10 (s, 252H; TiPS) ppm; 13 C NMR (175 MHz, CD 2 Cl 2, 303 K): =156.22, , , , , , , , , , , , , , , , , , , , , , , , , , , , 91.49, 91.40, 18.81, ppm; MALDI-TOF (DCTB): m/z = 5080 [M + ], 5017 [M-2Cl] +, 3413 [M-1bpy-1Cl] +. [Ru(4,4 -bis(1,4-diphenyl-2,3-((p-ethynyl)phenyl)phenyl)-2,2 -bipyridyl) 3 ]Cl 2 (20). To a solution of 19 (0.110 g, mmol) in THF (2 ml) was added dropwise a solution of TBAF (0.082 g, mmol) in THF (2 ml). The reaction was stirred at RT for 1 h and then quenched with water. The THF was evaporated in vacuo and the residue extracted with dichloromethane/water (3 x). The organic layers were combined, washed with brine and dried over MgSO 4. After evaporation of the solvent the pure product was isolated by column chromatography on silica using dichloromethane/meoh (20/1) as an eluent. 20 was isolated as an intense red solid. Yield: g, 82%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): =7.72 (n.r., 6H; bpy-h3), 7.63 (s, 6H), 7.28 (d, 6H, 3 J(H,H)=5.9 Hz; bpy-h6), (n.r., 18H), (n.r., 12H), 7.14 (dd, 6H, 3 J(H,H)=5.9 Hz; bpy-h5), 7.10 (d, 12H, 3 J(H,H)=8.5 Hz), 7.05 (d, 12H, 3 J(H,H)=8.4 Hz), (n.r., 42H), 6.77 (d, 12H, 3 J(H,H)=8.4 Hz), 3.06 (s, 6H; C C-H), 3.04 (6H; C C-H) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 303 K): = (1C, bpy-c2), (1C, bpy-c4), (1C, bpy-c6), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (1C), (4C), (2C), (1C), (2C), (2C), (1C, bpy-c5), (2C), (1C), (1C), (1C), (1C), (1C; bpy-c3), (1C), (1C), (2C; C C), 77.69, (2C, C C-H) ppm; MALDI-TOF (DCTB): m/z = 3144 [M-2Cl] +. [Ru(4,4 -bis([g2](tipsethynyl) 4 )-2,2 -bipyridyl) 3 ]Cl 2 (21). A mixture of 20 (0.070 g, mmol) and 11 (0.242 g, mmol) in ethylene glycol (3 ml) and o-xylene (2 ml) was stirred at 141 C for 3 d. After cooling to RT water was added and the mixture was extracted with dichloromethane (3 x). The combined organic layers were washed with brine and dried over MgSO 4. After evaporation of the solvent the remaining dark 9

11 residue was chromatographed on silica with dichloromethane/methanol (20/1) to give 21 as a red powder. Yield: g, 55% 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =7.63 (s, 6H; bpy- H3), 7.52 (s, 6H), 7.41 (s, 6H), 7.34 (s, 6H), (n.r., 60H), (n.r., 24H), (n.r., 36H), 7.04 (n.r., 6H; bpy-h6), 7.02 (2d, 24H, 3 J(H,H)=6.5 Hz), (n.r., 18H), 6.88 (n.r., 18H), (n.r., 114H), 6.67 (d, 12H, 3 J(H,H)=7.5 Hz), 6.53 (d, 12H, 3 J(H,H)=7.9 Hz), 6.48 (d, 12H, 3 J(H,H)=7.5 Hz), 1.10 (3s, 378H; TiPS), 1.09 (s, 126H; TiPS) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 303 K): =156.15, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 91.07, 91.04, 91.00, 90.94, 18.80, ppm; MALDI-TOF (DCTB): m/z = [M- 2Cl] +, 7901 [M-1bpy-1Cl] +, 5874 [ M] 2+, 4001 [M-2bpy-2Cl] +. [Ru(4,4 -bis([g2](ethynyl) 4 )-2,2 -bipyridyl) 3 ]Cl 2 (22). A solution of TBAF (0.057 g, mmol) in THF (2 ml) was added dropwise to a solution of 21 (0.085 g, mmol) in THF (2 ml) and the resulting mixture was stirred at RT for 1 h before water was added. The THF was removed in vacuo and the residue was extracted with dichloromethane (3 x). The organic layers were combined, washed with brine (4x) and dried over MgSO 4. After evaporation of the solvent the residue was dissolved in a small amount of dichloromethane and the product was precipitated into n-pentane to give 22 as a red powder which was collected on a frit. Yield: g, 62%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =7.58 (s, 6H; bpy-h3), 7.53 (s, 6H), 7.43 (s, 6H), 7.38 (s, 6H), 7.25 (d, 6H, 3 J(H,H)=5.1 Hz; bpy-h6), 7.18 (n.r., 54H), 7.13 (n.r., 24H), (n.r., 42H), 7.02 (2d, 24H, 3 J(H,H)=5.8 Hz), (n.r., 36H), (n.r., 42H), 6.74 (n.r., 60H), 6.70 (n.r., 12H), 6.68 (d, 12H, 3 J(H,H)=7.4 Hz), 6.55 (d, 12H, 3 J(H,H)=7.4 Hz), 6.49 (d, 12H, 3 J(H,H)=7.4 Hz), 3.04 (2s, 12H; C C-H), 3.02 (s, 6H; C C-H), 3.00 (s, 6H; C C-H) ppm; 13 C NMR (175 MHz, CD 2 Cl 2, 303 K): =156.14, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 83.80, 77.43, ppm; MALDI-TOF (DCTB): m/z = 8059 [M + ], 7998 [M-2Cl] +, 5428 [M-1bpy-1Cl] +, 5402 [M-1bpy-2Cl] +. 10

12 [Ru([4,4 -bis([g3](tipsethynyl) 8-2,2 -bipyridyl) 3 ]Cl 2 (23). A mixture of 22 (0.023 g, mmol) and 11 (0.064 g, mmol) in o-xylene and ethylene glycol was stirred for 4d at 140 C. After cooling to RT, the mixture was extracted with water into dichloromethane. After evaporation of the solvent, the residue was dried in vacuo before it was chromatographed on silica with dichloromethane/methanol (20/1) to give 23 as a orange powder. Yield: g, 81%. 1 H NMR (500 MHz, CD 2 Cl 2, 303 K): = 7.59 (n.r., 6H, bpy-h3), 7.48 (n.r., 6H), 7.40 (2s, 12H), 7.35 (3s, 18H), 7.28 (s, 6H), (n.r., 768H), (1008H, TiPS) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 303 K): =156.14, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 91.02, 90.94, 18.83, ppm; MALDI-TOF (DCTB): m/z = [M-2Cl] +, [M- 1bpy-1Cl] +, 8498 [M-2bpy-1Cl] +. [Ru(4,4 -bis(1,2,3,4-tetraphenylphenyl)-2,2 -bipyridyl) 3 ](methyl orange) 2 (24). A solution of 16 (0.020 g, mmol) in dichloromethane (1 ml) was vigorously stirred with a solution of sodium methyl orange (0.025 g, mmol) in water (1 ml) for 3 d. Then dichloromethane (10 ml) and water (10 ml) were added and the layers were separated. The organic phase was washed with water (3 x 10 ml) and dried over MgSO 4. Evaporation of the solvent gave 24. Yield: g, 91%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =7.82 (d, 4H, 3 J(H,H)=9.1 Hz; MO-H), 7.70 (d, 6H, 4 J(H,H)=1.7 Hz; bpy-h3), 7.66 (d, 4H, 3 J(H,H)=8.4 Hz; MO-H), 7.59 (s, 6H), 7.58 (d, 4H, 3 J(H,H)=8.4 Hz; MO-H); 7.27 (d, 6H, 3 J(H,H)=5.9 Hz; bpy-h6), 7.18 (s, 30H), 7.13 (dd, 6H, 3 J(H,H)= 5.9 Hz, 3 J(H,H)=1.8 Hz; bpy-h5), (n.r., 18H), (n.r., 72H), 7.76 (d, 4H, 3 J(H,H)=9.1Hz; MO-H), 1.52 (s, 12H) ppm; 13 C NMR (75 MHz, CD 2 Cl 2, 300 K): =156.19, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ppm. [Ru(4,4 -bis(1,2,3,4-tetraphenylphenyl)-2,2 -bipyridyl) 3 ] (PF 6 ) 2 (25). A solution of 16 (0.175 g, mmol) in water (1 ml) was added dropwise to a solution of NH 4 PF 6 (0.100 g, mmol) in water (100 ml). The precipitate was collected, washed with 11

13 water and dried in vacuo. Yield: g, 92%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =7.71 (n.r., 6H; bpy-h3), 7.58 (s, 6H), 7.19 (n.r., 30H), 7.12 (d, 6H, 3 J (H,H)=5.6 Hz; bpy-h), 7.10 (d, 6H, 3 J (H,H)=5.6 Hz; bpy-h), 6.97 (n.r., 18H), (n.r., 48H), 6.83 (n.r., 18H), 6.80 (n.r., 6H) ppm; 13 C NMR (175 MHz, CD 2 Cl 2, 303 K): =156.20, , , , , , , , , , , , , , , , , , , , , , , , , , , , ppm; MALDI-TOF (DCTB): m/z (%): 3142 (100) [M + ], 2998 [M- PF 6 ] +, 2853 [M-2PF 6 ] +. [Ru(4,4 -bis(1,2,3,4-tetraphenylphenyl)-2,2 -bipyridyl) 3 ](BPh 4 ) 2 (26). A solution of 16 (0.020 g, mmol) in chloroform (1 ml) was vigorously stirred with a solution of sodium methyl orange (0.025 g, mmol) in water (1 ml) for 3 d. Then dichloromethane (10 ml) and water (10 ml) were added and the layers were separated. The organic phase was washed with water (3 x 10 ml) and dried over MgSO 4. The product was observed upon evaporation of the solvent. Yield: g, 88%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =8.27 (d), 7.71 (n.r.), 7.69 (n.r.), 7.61 (d, 3 J(H,H)=8.3 Hz), 7.57 (s), 7.45 (t), 7.36 (d, 3 J(H,H)=8.7 Hz), 7.27 (d, 3 J(H,H)=7.6 Hz), 7.25 (n.r.), 7.18 (s), 7.11 (d, 3 J(H,H)=5.8 Hz), (n.r.), (n.r.) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 303 K): =156.75, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ppm. Bis(4,4 -(bis(triisopropylsilylethynyl)-2,2 -bipyridyl)rutheniumdichloride (27). Ru(DMSO) 4 Cl 2 (0.070 g, mmol) and 2 (0.150 g, mmol) were dissolved in dry DMF (5 ml) and the mixture was heated to 140 C for 8 h. The DMF was removed in vacuo and the remaining dark solid was chromatographed on silica using dichloromethane/petroleum ether (4/1) and then dichloromethane. Evaportion of the solvent gave 27 as a dark green solid. Yield: g, 64%. 1 H NMR (250 MHz, CD 2 Cl 2, 300 K): = (d, 2H, 3 J(H,H)=5.6 Hz, H6a), 8.19 (d, 2H, 4 J(H,H)=1.3 Hz, H3a), 8.04 (d, 2H, 4 J(H,H)=1.4 Hz, H3b), 7.62 (dd, 2H, 3 J(H,H)=6.0 Hz, 4 J(H,H)=1.7 Hz, H5a), 7.53 (d, 2H, 3 J(H,H)=6.0 Hz, H6b), 6.95 (dd, 2H, 3 J(H,H)=1.8 Hz, 3 J(H,H)=6.0 Hz), H5b), 1.20 (s, 18H, CH 3 ), 1.19 (s, 3H, CH), 1.11 (s, 18H, CH 3 ), 1.10 (s, 3H, CH 3 ) ppm; 13 C NMR (75 MHz, CD 2 Cl 2, 300 K): =160.0, 157.9, 154.1, 152.2, 130.0, 128.7, 128.2, 127.6, 124.7, 124.4, 12

14 103.8, 103.5, 100.5, 100.2, 18.8, 18.7, 11.7, 11.5 ppm; FDMS (80 ev): m/z (%) = (100) [M + ]. [Ru(4,4 -(bis(triisopropylsilylethynyl)-2,2 -bipyridyl) 2 (4,4 -bis[g2]-2,2 -bipyridyl) 3 ]Cl 2 (28). 6 (0.043 g, mmol) and 27 (0.024 g, mmol) were dissolved in a mixture of chloroform (1.5 ml) and EtOH (1.5 ml) for 6 d. The solvent was evaporated and the residue was chromatographed twice on silica using dichloromethane/methanol (20/1) as an eluent. After evaporation of the solvent, 28 was obtained as a red solid. Yield: 28 mg, 46%. 1 H NMR (700 MHz, CD 2 Cl 2, 303 K): =8.23 (s, 2H), 8.21 (s, 2H), 8.01 (d, 2H, 3 J(H,H)=5.8 Hz), 7.94 (d, 2H, 3 J(H,H)=5.4 Hz), 7.61 (n.r., 2H), 7.57 (n.r. 4H), 7.54 (d, 2H, 3 J(H,H)=5.4 Hz), (n.r., 4H), 7.35 (n.r., 2H), (n.r., 32H), (n.r., 78 H), (n.r., 8H), (6s, 84H) ppm; 13 C NMR (125 MHz, CD 2 Cl 2, 300 K): =156.37, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 97.98, 97.96, 96.20, 18.84, 18.77, 11.69, ppm; MALDI-TOF (dithranol): m/z = 3574 [M-2Cl] +. 13

15 Figure S1. MALDI-TOF of the [G3] 2,2 -bipyridyl dendron 7 (matrix: dithranol). Figure S2. MALDI-TOF of the [G3] tris(2,2 -bipyridyl)ruthenium dendrimer 18 (matrix: 2- [(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile, 10% laser intensity). 14

16 Figure S3. MALDI-TOF of the G3 tris(2,2 -bipyridyl)ruthenium dendrimer 23 (matrix: 2- [(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile, 20% laser intensity). 15

17 Figure S4. 1 H NMR spectra of 2,2 -bipyridyl dendrons 5 8 and in CD 2 Cl 2 (5, 6, 8, 13, 15: 500 MHz, 303 K; 7: 700 MHz, 303 K; 13: 300 MHz, 300 K; 14: 250 MHz, 300 K. 16

18 Figure S5. 1 H NMR spectra of tris(2,2 -bipyridyl)ruthenium dendrimers (16, 19, 21, 22: 700 MHz, CD 2 Cl 2, 303 K; 17, 18, 20: 500 MHz, CD 2 Cl 2, 303 K; 23: 500 MHz, CDCl 3, 303 K. 17

19 M olar Extinction Coefficien t [m 2 mo l -1 ] Figure S6. UV/vis absorption spectra of 16-19, 21, and 23 (10-5 M in chloroform) 1 H NMR PFG (Pulse Field Gradient) self-diffusion measurements The 1 H pulse sequence in the 2D-DOSY (Diffusion Ordered SpectroscopY) for diffusion, used double stimulated echo (bipolar gradients) for convection compensation. [7,8] Measurements were performed on a Bruker DRX 700 spectrometer, operating at 700 MHz for protons. The experiments were done with a 5 mm dual 1 H/ 13 C z-gradient probe with a gradient strength of [G/cm]. For the calibration of the gradient strength, a sample of 2 H 2 O/ 1 H 2 O was measured at a defined temperature and compared with the literature diffusion coefficient of 2 H 2 O/ 1 H 2 O, generating a new correct gradient strength value. The temperature was kept at K and defined with the methanol 1 H NMR standard from Bruker. In this work, the gradient strength was varied in 32 steps from 2 to 100%. The diffusion time d20 was optimized at 160 ms and the gradient length p30 to 1.4 ms. As an internal frequency lock, the deuterons of the solvent CD 2 Cl 2 were used, which had a viscosity of = 0.43 mpa s at K. The concentration of dendrimer 18 was 1 mg/ml in CD 2 Cl 2. 18

20 Figure S7. 1 H 2D-DOSY NMR of dendrimer 18 in CD 2 Cl 2. The measured dendrimer 18 -logarithmic value of the diffusion coefficient was -9,729 (Figure S7). Using the Stokes-Einstein equation (Equation S1), the hydrodynamic radius of dendrimer 18, assuming spherical geometry, was determined to be 2.4 nm. kt D = 6 r S r S kt = 6 D Equation S1. Stokes-Einstein equation; D is the diffusion coefficient [m 2 /s], k Boltzmann s constant, T temperature [K], viscosity, and r s the hydrodynamic radius. References: [1] L. Ulmer, H. G. Torres-Garcia, J. Mattay, H. Luftmann, Eur. J. Mass Spectrom. 2000, 6, 49. [2] X. F. Duan, X. H. Li, F. Y. Li, C. H. Huang, Synthesis 2004, 2004, [3] I. P. Evans, A. Spencer, G. Wilkinson, J. Chem. Soc. Dalton Trans. 1973, 204. [4] F. Morgenroth, E. Reuther, K. Müllen, Angew. Chem., Int. Ed. 1997, 36, 629. [5] U. M. Wiesler, K. Müllen, Chem. Commun. 1999, 2293,

21 [6] Andreitchenko, E. V.; Clark, C. G., Jr.; Bauer, R. E.; Lieser, G.; Müllen, K., Angew. Chem. 2005, 117, 6506; Angew. Chem. Int. Ed. 2005, 44, [7] A. Jerschow, N. Müller, J. Magn. Reson. A 1996, 123, [8] A. Jerschow, N. Müller, J. Magn. Reson. A 1997, 125,