Abstract
Rhodium(III) polypyridine complexes and their cyclometalated analogues display photophysical properties of considerable interest, both from a fundamental viewpoint and in terms of the possible applications. In mononuclear polypyridine complexes, the photophysics and photochemistry are determined by the interplay between LC and MC excited states, with relative energies depending critically on the metal coordination environment. In cyclometalated complexes, the covalent character of the C–Rh bonds makes the lowest excited state classification less clear cut, with strong mixing of LC, MLCT, and LLCT character being usually observed. In redox reactions, Rh(III) polypyridine units can behave as good electron acceptors and strong photo-oxidants. These properties are exploited in polynuclear complexes and supramolecular systems containing these units. In particular, Ru(II)-Rh(III) dyads have been actively investigated for the study of photoinduced electron transfer, with specific interest in driving force, distance, and bridging ligand effects. Among systems of higher nuclearity undergoing photoinduced electron transfer, of particular interest are polynuclear complexes where rhodium dihalo polypyridine units, thanks to their Rh(III)/Rh(I) redox behavior, can act as two-electron storage components. A large amount of work has been devoted to the use of Rh(III) polypyridine complexes as intercalators for DNA. In this role, they have proven to be very versatile, being used for direct strand photocleavage marking the site of intercalation, to induce long-distance photochemical damage or dimer repair, or to act as electron acceptors in long-range electron transfer processes.
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References
Carassiti V, Balzani V (1970) Photochemistry of Coordination Compounds. Academic Press, New York
Kalyanasundaram K (1992) Photochemistry of Polypyridine and Porphyrin Complexes. Academic Press, London
Balzani V, Juris A, Venturi M, Campagna S, Serroni S (1996) Chem Rev 96:759
Hannon MJ (1997) Coord Chem Rev 162:477
Scandola F, Chiorboli C, Indelli MT, Rampi MA (2001) Covalently linked systems containing metal complexes. In: Balzani V (ed) Electron Transfer in Chemistry, Vol III, Chap 2.3. Wiley-VCH, Weinheim, p 337
Chiorboli C, Indelli MT, Scandola F (2005) Top Curr Chem 257:63
Ford PC (1983) J Chem Ed 60:829
Ford PC, Wink D, DiBenedetto J (1983) Prog Inorg Chem 40:213
Miller DB, Miller PK, Kane-Maguire NAP (1983) Inorg Chem 22:3831
Frink ME, Ford PC, Skibsted LH (1984) Acta Chem Scand A38:795
Skibsted LH, Hancock MP, Magde D, Sexton DA (1984) Inorg Chem 23:3735
Skisbsted LH (1985) Coord Chem Rev 64:343
Kane-Maguire NAP, Wallace KC, Cobranchi DP, Derrick JM, Speece DG (1986) Inorg Chem 25:2101
Skibsted LH, Hancock MP, Magde D, Sexton DA (1987) Inorg Chem 26:1708
McClure LJ, Ford PC (1992) J Phys Chem 96:6640
Carlos RM, Frink ME, Tfouni E, Ford PC (1992) Inorg Chim Acta 193:159
Islam K, Ikeda AN, Nozaki KT, Ohno T (1998) J Chem Phys 109:4900
Forster LS, Rund JV (2003) Inorg Chem Commun 6:78
Coppens P, Gerlits O, Vorontsov II, Kovalevsky AY, Chen Y-S, Graber T, Novozhilova IV (2004) Chem Commun, p 2144
Miskowski VM, Rice SF, Gray HB, Milder SJ (1993) J Phys Chem 97:4277
Bradley PM, Bursten BE, Turro C (2001) Inorg Chem 40:1376
Cotton FA, Lin C, Murillo CA (2001) Acc Chem Res 34:759
Lo Schiavo S, Serroni S, Puntoriero F, Tresoldi G, Piraino P (2002) Eur J Inorg Chem 79
Cooke MW, Hanan GS, Loiseau F, Campagna S, Watanabe M, Tanaka Y (2005) Angew Chem Int Ed 44:4881
Heyduk AF, Macintosh AM, Nocera DG (1999) J Am Chem Soc 121:5023
Heyduk AF, Nocera DG (2001) Science 293:1639
Gray TG, Nocera DG (2005) Chem Commun, p 1540
Hillis JE, De Armond MK (1971) J Lumin 4:273
Carstens DHW, Crosby GA (1970) J Mol Spectrosc 34:113
Crosby GA, Elfring WH Jr (1976) J Phys Chem 80:2206
De Armond MK, Hillis JE (1971) J Chem Phys 54:2247
Humbs W, Yersin H (1996) Inorg Chem 35:2220
Humbs W, Strasser J, Yersin H (1997) J Lumin 72–74:677
Indelli MT, Carioli A, Scandola F (1984) J Phys Chem 88:2685
Bolletta F, Rossi A, Barigelletti F, Dellonte S, Balzani V (1981) Gazz Chim Ital 111:155
Ohno T, Kato S (1984) Bull Chem Soc Jpn 57:3391
Nishizawa M, Suzuki TM, Sprouse S, Watts RJ, Ford PC (1984) Inorg Chem 23:1837
Indelli MT, Scandola F (1990) Inorg Chem 29:3056
Brozik JA, Crosby GA (2005) Coord Chem Rev 249:1310
Broomhead JA, Grumley W (1968) Chem Commun, p 1211
Muir MM, Huang WL (1973) Inorg Chem 12:1831
Loganathan D, Rodriguez JH, Morrison H (2003) J Am Chem Soc 125:5640
Menon EL, Perera R, Navarro M, Kuhn RJ, Morrison H (2004) Inorg Chem 43:5373–5381
Huang WL, Lee JR, Shi SY, Tsai CY (2003) Trans Met Chem 28:381
Tseng MC, Li FK, Huang JH, Su WL, Wang SP, Huang WL (2006) Inorg Chim Acta 359:401
Calvert JM, Caspar JV, Binstead RA, Westmoreland TD, Meyer TJ (1982) J Am Chem Soc 104:6620
Frink ME, Sprouse SD, Goodwin HA, Watts RJ, Ford PC (1988) Inorg Chem 27:1283
Watts RJ, Van Houten J (1978) J Am Chem Soc 100:1718
Westra J, Glasbeek M (1992) J Lumin 53:92
Turro C, Evenzahav A, Bossmann SH, Barton JK, Turro NJ (1996) Inorg Chim Acta 243:101
Burke HM, Gallagher JF, Indelli MT, Vos JG (2004) Inorg Chim Acta 357:2989
Shinozaki K, Takahashi N (1996) Inorg Chem 35:3917
Fujita E, Brunschwig BS, Creutz C, Muckerman JT, Sutin N, Szalda D, van Eldik R (2006) Inorg Chem 45:1595
Martin B, McWhinnie WR, Waind GM (1961) J Inorg Nucl Chem 23:207
Chou M, Creutz C, Mahajan D, Sutin N, Zipp AP (1982) Inorg Chem 21:3989
Mulazzani QG, Venturi M, Hoffman MZ (1982) J Phys Chem 86:242
Schwarz HA, Creutz C (1983) Inorg Chem 22:707
Yan SG, Brunschwig BS, Creutz C, Fujita E, Sutin N (1998) J Am Chem Soc 120:10553
Maestri M, Balzani V, Deuschel-Cornioley C, von Zelewsky A (1992) Adv Photochem 17:1
Colombo MG, Brunold TC, Riedener T, Guedel HU, Fortsch M, Buergi H-B (1994) Inorg Chem 33:545
Constable EC, Leese TA (1990) Polyhedron 9:1613
Maeder U, von Zelewsky A, Stoeckli-Evans H (1992) Helv Chim Acta 75:1320
Maestri M, Sandrini D, Balzani V, Mader U, von Zelewsky A (1987) Inorg Chem 26:1323
Ohsawa Y, Sprouse S, King KA, De Armond MK, Hanck KW, Watts RJ (1987) J Phys Chem 91:1047
Zilian A, Maeder U, von Zelewski A, Guedel HU (1989) J Am Chem Soc 111:3855
Zilian A, Guedel HU (1991) Coord Chem Rev 111:33
Ghizdavu L, Lentzen O, Schumm S, Brodkorb A, Moucheron C, Kirsch-De Mesmaeker A (2003) Inorg Chem 42:1935
Hay PJ (2002) J Phys Chem A 106:1634
Polson M, Ravaglia M, Fracasso S, Garavelli M, Scandola F (2005) Inorg Chem 44:1282
Barigelletti F, Sandrini D, Maestri M, Balzani V, von Zelewsky A, Chassot L, Jolliet P, Maeder U (1988) Inorg Chem 27:3644
Lo KK-W, Li C-K, Lau K-W, Zhu N (2003) Dalton Trans 24:4682
Sandrini D, Maestri M, Balzani V, Mader U, von Zelewsky A (1988) Inorg Chem 27:2640
Calogero G, Giuffrida G, Serroni S, Ricevuto V, Campagna S (1995) Inorg Chem 34:541
Didier P, Ortmans I, Kirsch-De Mesmaeker A, Watts RJ (1993) Inorg Chem 32:5239
Van Diemen JH, Hage R, Haasnoot JG, Lempers HEB, Reedijk J, Vos JG, De Cola L, Barigelletti F, Balzani V (1992) Inorg Chem 31:3518
Ortmans I, Didier P, Kirsch-De Mesmaeker A (1995) Inorg Chem 34:3695
Petitjean A, Puntoriero F, Campagna S, Juris A, Lehn J-M, (2006) Eur J Inorg Chem 3878
Kew G, Hanck K, DeArmond MK (1975) J Phys Chem 79:1828
Ballardini R, Varani G, Balzani V (1980) J Am Chem Soc 102:1719
Indelli MT, Ballardini R, Scandola F (1984) J Phys Chem 88:2547
Lehn J-M, Sauvage J-P (1977) Nouv J Chim 1:449
Chan S-F, Chou M, Creutz C, Matsubara T, Sutin N (1981) J Am Chem Soc 103:369
Creutz C, Keller AD, Sutin N, Zipp A P (1982) J Am Chem Soc 104:3618
Indelli MT, Bignozzi CA, Harriman A, Schoonover JR, Scandola F (1994) J Am Chem Soc 116:3768
Yoshimura A, Nozaki K, Ohno T (1997) Coord Chem Rev 159:375
Furue M, Hirata M, Kinoshita S, Kushida T, Kamachi M (1990) Chem Lett 2065
Collin J-P, Gavina P, Heitz V, Sauvage J-P (1998) Eur J Inorg Chem :1
Welter S, Salluce N, Belser P, Groeneveld M, De Cola L (2005) Coord Chem Rev 249:1360
Welter S, Lafolet F, Cecchetto E, Vergeer F, De Cola L (2005) Chem Phys Chem 6:2417
Barigelletti F, Flamigni I (2000) Chem Soc Rev 29:1
Indelli MT, Scandola F, Flamigni L, Collin J-P, Sauvage J-P, Sour A (1997) Inorg Chem 36:4247
Indelli MT, Chiorboli C, Flamigni L, De Cola L, Scandola F (2007) Inorg Chem (in press)
McConnell HM (1961) J Chem Phys 35:508
Newton MD (1991) Chem Rev 91:767
Paddon-Row MN (2001) Covalently linked systems based on organic components. In: Balzani V (ed) Electron Transfer in Chemistry, Vol III, Chap 2.1. Wiley-VCH, Weinheim, p 179
Helms A, Heiler D, McLendon G (1992) J Am Chem Soc 114:6227
Weiss EA, Ahrens MJ, Sinks LE, Gusev AV, Ratner MA, Wasielewsi MR (2004) J Am Chem Soc 126:5577
Wold DJ, Haag R, Rampi MA, Frisbie CD (2002) J Phys Chem B 106:2814
Toutounji MM, Ratner MA (2000) J Phys Chem A 104:8566
Tour JM, Lamba JJS (1993) J Am Chem Soc 115:4935
Tsuzuki K, Tanabe J (1991) J Phys Chem 95:139
Kalyanasundaram K, Graetzel M, Nazeeruddin MK (1992) J Phys Chem 96:5865
Lee J-D, Vrana LM, Bullock ER, Brewer KJ (1998) Inorg Chem 37:3575
Kew G, DeArmond K, Hanck K (1974) J Phys Chem 78:727
Collin J-P, Harriman A, Heitz V, Odobel F, Sauvage J-P (1994) J Am Chem Soc 116:5679
Wasielewski MR (1992) Chem Rev 92:435
Gust D, Moore TA, Moore AL (2001) Covalently linked systems containing porphyrin units. In: Balzani V (ed) Electron Transfer in Chemistry, Vol III, Chap 2.2. Wiley-VCH, Weinheim, p 273
Larson SL, Elliott CM, Kelley DF (1995) J Phys Chem 99:6530
Huynh MHV, Dattelbaum DM, Meyer TJ (2005) Coord Chem Rev 249:457
Baranoff E, Collin J-P, Flamigni L, Sauvage J-P (2004) Chem Soc Rev 33:147
Ronco SE, Thompson DW, Gahan SL, Petersen JD (1998) Inorg Chem 37:2020
Indelli MT, Polo E, Bignozzi CA, Scandola F (1991) J Phys Chem 95:3889
Kleverlaan CJ, Indelli MT, Bignozzi CA, Pavanin LA, Scandola F, Hasselman GM, Meyer GJ (2000) J Am Chem Soc 122:2840
Balzani V, Scandola F (1991) Supramolecular Photochemistry. Horwood, Chichester
Konduri R, Ye H, MacDonnell FM, Serroni S, Campagna S, Rajeshwar K (2002) Angew Chem Int Ed 41:3185
Chiorboli C, Fracasso S, Ravaglia M, Scandola F, Campagna S, Wouters K, Konduri R, MacDonnell F (2005) Inorg Chem 44:8368
Heyduk AF, Nocera DG (2001) Science 293:1639
Esswein A, Veige A, Nocera D (2005) J Am Chem Soc 127:16641
Chang CC, Pfennig B, Bocarsly AB (2000) Coord Chem Rev 208:33
Watson DF, Tan HS, Schreiber E, Mordas CJ, Bocarsly AB (2004) J Phys Chem A 108:3261
Rau S, Schfer B, Gleich D, Anders E, Rudolph M, Friedrich M, Gorls H, Henry W, Vos JG (2006) Angew Chem Int Ed 45:6215
Ozawa H, Haga M, Sakai K (2006) J Am Chem Soc 128:4926
Molnar SM, Nallas G, Bridgewater JS, Brewer KJ (1994) J Am Chem Soc 116:5206
Nallas GNA, Jones SW, Brewer KJ (1996) Inorg Chem 35:6974
Molnar SM, Jensen GE, Vogler LM, Jones SW, Laverman L, Bridgewater JS, Richter MM, Brewer KJ (1994) J Photochem Photobiol A Chem 80:315
Swavey S, Brewer KJ (2002) Inorg Chem 41:4044
Elvington M, Brewer KJ (2006) Inorg Chem 45:5242
Barton JK (1986) Science 233:727
Pyle AM, Barton JK (1990) In: Lippard SJ (ed) Progress in Inorganic Chemistry: Bioinorganic Chemistry, Vol 38. Wiley, New York, p 413
Erkkila KE, Odom DT, Barton JK (1999) Chem Rev 99:2777
Jennette KW, Lippard SJ, Vassiliades GA, Bauer WR (1974) Proc Natl Acad Sci USA 71:3839
Crotz AH, Hudson BP, Barton JK (1993) J Am Chem Soc 115:12577
Pyle AM, Chiang MY, Barton JK (1990) Inorg Chem 29:4487
David SS, Barton JK (1993) J Am Chem Soc 115:2984
Crotz AH, Kuo LY, Barton JK (1993) Inorg Chem 32:5963
Collins J-C, Shield JK, Barton JK (1994) J Am Chem Soc 116:9840
Crotz AH, Barton JK (1994) Inorg Chem 33:1940
Hudson BP, Barton JK (1998) J Am Chem Soc 120:6877
Crotz AH, Kuo LY, Shields TP, Barton JK (1993) J Am Chem Soc 115:3877
Sitlani A, Dupureur C, Barton JK (1993) J Am Chem Soc 115:12589
Sitlani A, Long EC, Pyle AM, Barton JK (1992) J Am Chem Soc 114:2303
Kisko J, Barton JK (2000) Inorg Chem 39:4942
Turro C, Hall DB, Chen W, Zuilhof H, Barton JK, Turro NJ (1998) J Phys Chem A 102:5708
Holmlin RE, Dandliker PJ, Barton KJ (1997) Angew Chem Int Ed 36:2714
Hudson BP, Dupureur CM, Barton JK (1995) J Am Chem Soc 117:9379
Kielkopf CL, Erkkila KE, Hudson BP, Barton JK, Rees DC (2000) Nat Struct Biol 7:117
Pyle AM, Morii T, Barton JK (1990) J Am Chem Soc 112:9432
Sardesai NJ, Zimmermann, Barton JK (1994) J Am Chem Soc 116:7502
Terbrueggen RH, Johann T W, Barton JK (1998) Inorg Chem 37:6874
Jackson BA, Barton JK (1997) J Am Chem Soc 119:12986
Jackson BA, Alekseyev VY, Barton JK (1999) Biochemistry 38:4655
Kisko JL, Barton JK (2000) Inorg Chem 39:4942
Holder AA, Swavey A, Brewer KJ (2004) Inorg Chem 43:303
Swavey S, Brewer KJ (2002) Inorg Chem 41:6196
Lewis FD (2001) In: Balzani V (ed) Electron Transfer in Chemistry, Vol III, Chap 1.5. Wiley/VCH, Weinheim, p 105
Stemp EDA, Barton JK (1996) In: Sigel A, Sigel H (eds) Metal Ions in Biological systems, Vol 33. Marcel Dekker, New York, p 325
Murphy CJ, Arkin MR, Jenkins Y, Ghatlia ND, Bossmann S, Turro NJ, Barton JK (1993) Science 262:1025
Friedman AE, Chambron JC, Sauvage JP, Turro NJ, Barton JK (1990) J Am Chem Soc 112:4960
Hort C, Lincoln P, Norden B (1993) J Am Chem Soc 115:3448
Arkin MR, Stemp EDA, Holmlin RE, Barton JK, Hormann A, Olson EJC, Barbara PF (1996) Science 273:475
Olson EJC, Hu D, Hormann A, Barbara PF (1997) J Phys Chem B 101:299
Lincoln P, Tuite E, Norden B (1997) J Am Chem Soc 119:1454
Saito I, Takayama M, Sugiyama H, Nakatani K (1995) J Am Chem Soc 117:6406
Kittler L (1980) J Electroanalyt Chem 116:503
Hall DB, Holmlin RE, Barton JK (1996) Nature 382:731
Nunez ME, Hall DB, Barton JK (1999) Chem Biol 6:85
Dandliker PJ, Holmlin RE, Barton JK (1997) Science 275:1465
Dandliker PJ, Nunez ME, Barton JK (1998) Biochemistry 37:6491
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Indelli, M.T., Chiorboli, C., Scandola, F. (2007). Photochemistry and Photophysics of Coordination Compounds: Rhodium. In: Balzani, V., Campagna, S. (eds) Photochemistry and Photophysics of Coordination Compounds I. Topics in Current Chemistry, vol 280. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2007_137
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